JP2008298820A - Composition for optical filter, optical filter using the same and front filter for display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for optical filter containing squarylium metal chelate compound, a pigment with favorable hue in color reproduction in a visible range and high robustness, such as weather resistance, preservability, and to provide the optical filter and a front filter for display containing the pigment. <P>SOLUTION: The composition for optical filter contain squarylium metal chelate pigment represented by a general formula (1): M[(SQ)l(W<SB>1</SB>)m(W<SB>2</SB>)n]X. In the general formula (1), SQ is a specific squarylium compound represented by a general formula (2). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an optical filter composition containing a squarylium metal chelate compound, an optical filter using the same, and a front filter for a display.

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

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

  The color adjusting filter dye is required to have good absorption characteristics in the visible range, for example, having a large molar extinction coefficient, a small half-value width, and no side absorption.

  At the same time, from the viewpoint of filter production, high solubility in various organic solvents and high compatibility with binders are required.

  Further, since the display is assumed to be used for a long time, it is required to have high weather resistance, particularly high light resistance.

  In a plasma display, it is necessary to add a dye having absorption in the vicinity of 560 to 620 nm in order to improve the color purity or raise the color temperature.

  In addition, since this wavelength region includes light emission from neon gas in the panel, an optical filter that absorbs such unnecessary light emission is required.

  In response to such demands, various dyes have been proposed. Among them, squarylium dyes have excellent absorption characteristics such as a large molar extinction coefficient and a small half-value width, and optical filters using the same, A filter for plasma display has been proposed (see, for example, Patent Documents 1 and 2).

  In addition, it has been proposed to use a squarylium dye having an imino group as a substituent for a display filter (see, for example, Patent Document 3).

  However, the squarylium dye described in the above document has a problem that durability, particularly light resistance is not sufficient, and it is unsuitable for practical use.

  Furthermore, a complex of a squarylium compound having an imino group and a metal is also known (see Patent Document 4).

  However, this publication only exemplifies a mixture of the following structure A and a copper compound as a specific compound, and the compound is characterized by having absorption in the infrared region.

JP 2004-86133 A JP 2004-99711 A JP 2002-363434 A JP 2000-159776 A

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

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

  1. The composition for optical filters characterized by containing the squarylium metal chelate pigment | dye represented by following General formula (1).

General formula (1)
M [(SQ) l (W ₁ ) m (W ₂ ) n] X
(In the formula, M represents a metal ion. SQ represents a squarylium compound represented by the following general formula (2), W ₁ and W ₂ each independently represent a monodentate or bidentate ligand, and 1 is an integer of 1 or more, m and n each represents an integer of 0 to 2, l + m + n ≧ 2, and X is a counter ion necessary for neutralizing the charge Represents.)

(In the formula, A represents an arbitrary organic group, B ₁ , B ₂ , B ₃ and B ₄ are carbon atoms or nitrogen atoms. When they are carbon atoms, they have a hydrogen atom or a substituent, and have an aromatic ring. Form.

R ₁ represents a hydrogen atom or a substituent. )
2. 2. The optical filter composition as described in 1 above, wherein the metal ion is at least one metal ion selected from cobalt, nickel, copper, and zinc.

  3. 3. An optical filter comprising the optical filter composition as described in 1 or 2 above.

  4). 4. The display front filter according to claim 3, wherein the optical filter is a display front filter.

  5). 5. The display front filter according to 4, wherein the display front filter is a plasma display front filter, and the dye represented by the following general formula (1) has an absorption maximum in a range of 560 to 620 nm. .

General formula (1)
M [(SQ) l (W ₁ ) m (W ₂ ) n] X
(In the formula, M represents a metal ion. SQ represents a squarylium compound represented by the following general formula (2), W ₁ and W ₂ each independently represent a monodentate or bidentate ligand, and 1 is an integer of 1 or more, m and n each represents an integer of 0 to 2, l + m + n ≧ 2, and X is a counter ion necessary for neutralizing the charge Represents.)

(In the formula, A represents an arbitrary organic group, B ₁ , B ₂ , B ₃ and B ₄ are carbon atoms or nitrogen atoms. When they are carbon atoms, they have a hydrogen atom or a substituent, and have an aromatic ring. Form.

R ₁ represents a hydrogen atom or a substituent. )

  As a result of various studies, the present inventors have found that an optical filter composition having excellent weather resistance and improved environmental preservation is provided.

  Further, the present inventors have an optical filter having an absorption maximum in the visible light region by the above means, excellent weather resistance, particularly high light resistance, and excellent environmental preservation and compatibility with a dispersant. We have also found that we can provide front filters for displays.

  The present invention will be described in detail below.

  The optical filter composition of the present invention contains a squarylium metal chelate compound composed of a squarylium compound and a metal ion as represented by the general formula (1), and has an absorption maximum in the visible light region. An optical filter composition characterized in that the composition further comprises an optical filter using the composition and a front filter for a display.

  The optical filter of the present invention is characterized by having at least one absorption maximum in the visible range, and transmits light of a specific color as known as a so-called color filter, and does not block the others. It is used to reduce or block the light in the wavelength range, and to transmit the other light.

  In the general formula (1), M represents a metal ion.

SQ represents the squarylium compound represented by the general formula (2), and X ₁ and X ₂ each independently represent a monodentate or bidentate ligand, which may be the same or different. l is an integer of 1 or more, m and n each represent an integer of 0 to 2, l + m + n ≧ 2, and X represents a counter ion necessary for neutralizing the charge.

In the general formula (2), A represents an arbitrary organic group, B ₁ , B ₂ , B ₃ and B ₄ are carbon atoms or nitrogen atoms, and when they are carbon atoms, they have a hydrogen atom or a substituent, An aromatic ring is formed. R ₁ represents a substituent.

  According to the study by the present inventors, the composition for optical filters in which various binders and metal ion-containing compounds and a squarylium compound having a specific structure are mixed has an absorption maximum in the visible light region, and has excellent weather resistance. I found it.

  Furthermore, the optical filter composition and optical filter of the present invention have good storage stability against changes in the surrounding environment such as temperature conditions, and are suitable for various optical members, particularly self-luminous displays. It became clear that it could be used.

  The squarylium compound having a specific structure in the present invention has a 6-membered aromatic ring bonded to the squaric acid skeleton as represented by the general formula (2), and this aromatic ring has a bonding position with the squaric acid skeleton. It is characterized by having an imino group at the adjacent position (o-position).

  The imino group here refers to a monosubstituted amino group.

  When a squarylium compound having a specific structure and a metal ion-containing compound are mixed, a squarylium metal chelate dye is generated by the interaction between the squarylium compound and the metal ion, and has an absorption maximum in the visible light region and further excellent weather resistance. It became clear to show.

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

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

  In general formula (1), M represents a metal ion.

  The metal M ion is not particularly limited as long as it is generally available. For example, copper, nickel, cobalt, zinc, aluminum, beryllium, iron, silver, chromium, manganese, iridium, vanadium, titanium, ruthenium, molybdenum, tin, Bismuth, osmium, magnesium, calcium, strontium, barium, gallium, germanium, platinum, gold, mercury and the like can be mentioned.

  It is preferable that it is an element contained in periodic table group 3-12 group, More preferably, it is a metal ion contained in periodic table group 7-12 group. The valence is preferably a divalent or trivalent metal.

  Among these, specifically, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, osmium, iridium or platinum are preferable, and copper, cobalt, nickel, or More preferably, it is zinc.

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

  In the present invention, a squarylium metal chelate compound having different metal ions may be used in combination.

In the general formula (2), R ₁ is a hydrogen atom or a substituent. Specific examples of the substituent represented by R ₁ include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, trifluoromethyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group etc.), alkenyl group ( For example, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heteroaryl group (eg, furyl group, thienyl group, pyridyl group) , Pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazo Aryl group, benzimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (also called heterocyclic group, for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, Methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (for example, , Phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclo Xylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.) , Aryloxycarbonyl groups (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), phosphoryl groups (eg, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl groups (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group) Butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylamino Nosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group) , Dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyl) Oxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylca) Carbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl) Group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2 -Pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexyl group) Ruureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc., sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2- Ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group) Group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino (For example, amino group, ethylamino group, dimethylamino group, butylamino group, dibutylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group) Examples include an azo group (for example, phenylazo), an alkylsulfonyloxy group (for example, methanesulfonyloxy), a cyano group, a nitro group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydroxyl group, and the like. R1 is preferably a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heteroaryl group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, an alkoxycarbonyl group, and an aryloxycarbonyl group. , Phosphoryl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonyloxy group, cyano group, preferably an alkyl group, A cycloalkyl group, an aryl group, a heterocyclic group, a heteroaryl group, an acyl group, an alkylsulfonyl group, and an arylsulfonyl group are preferable, and an acyl group, an alkylsulfonyl group, and an arylsulfonyl group are more preferable. These may be further substituted with the same substituent.

B ₁ , B ₂ , B ₃ and B ₄ are carbon atoms or nitrogen atoms. When they are carbon atoms, they have a hydrogen atom or a substituent and form a monocyclic 6-membered aromatic ring.

At this time, at least one of B ₁ , B ₂ , B ₃ and B ₄ is preferably a carbon atom, more preferably at least two are carbon atoms, and more preferably all are carbon atoms. .

When any of B ₁ , B ₂ , B ₃ and B ₄ is a carbon atom, it has a hydrogen atom or a substituent.

  The number of substituents is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more.

  Specific examples of the substituent include the same substituents represented by R1.

  Among these, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, heteroaryl groups, heterocyclic groups, alkoxy groups, cycloalkoxy groups, aryloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyl groups, acyloxy groups are preferred. Group, amide group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, amino group, azo group, alkylsulfonyloxy group, cyano group, nitro group, halogen atom, hydroxyl group, more preferably alkyl group, alkoxy group , Alkoxycarbonyl group, aryl group, acyl group, amide group, alkylsulfonyl group, arylsulfonyl group, amino group, cyano group, nitro group, halogen atom, hydroxyl group, more preferably alkyl group, alkoxy group, alkyl group, Examples include a xycarbonyl group, an aryl group, an acyl group, an amide group, an amino group, a cyano group, a nitro group, a halogen atom, and a hydroxyl group. From the viewpoint of improving solubility, at least one substituent has 4 or more carbon atoms. It is preferable to have a linear or branched alkyl group.

In particular, a hydroxyl group and an amino group are preferable as a substituent on B ₂ , and an amino group is more preferable. As the amino group, an alkylamino group and a dialkylamino group are preferable, and a dialkylamino group is particularly preferable. At this time, the substituents of the amino group may be the same or different, and may combine with each other or with substituents on B ₁ and B ₃ to form a ring.

  The ring formed at this time is preferably a heterocycle or a heteroaryl ring in which substituents of the amino group are bonded to each other, and the size of the ring formed is not particularly limited, but is 5 or 6 members. Is preferable, and a 5-membered ring is more preferable.

  The squarylium compound has a squaric acid skeleton at the center of the molecule, and has a structure having a substituent composed of an aromatic compound at two carbon atoms located on the diagonal line.

  If the two aromatic substituents are the same, this is referred to as a symmetric squarylium compound (or symmetric squarylium dye) for convenience, otherwise an asymmetric squarylium compound (or asymmetric squarylium dye). ).

  The squarylium compound used in the squarylium metal chelate compound of the present invention may be a symmetric squarylium compound or an asymmetric squarylium compound, but is preferably an asymmetric squarylium compound from the viewpoint of color tone adjustment.

A represents an arbitrary organic group, and examples of the organic group include the same groups as the substituents represented by R ₁ , R ₂ , R ₃ and R ₄ described above, preferably an aryl group or a heterocyclic ring. And a substituent represented by the group or the general formula (1-A).

In General Formula (1-A), A ₁ represents a 5-membered ring or an atomic group forming a 6-membered ring, and examples of the 5-membered ring represented by A ₁ include a pyrazolidinedione ring, an isoxazolone ring, and a pyrazolone. Ring, pyrrolidone ring (for example, 1H-pyrrole-2 (5H) -one ring), thioxathiazolidinone ring (for example, rhodanine ring, 4-thioxaimidazolidin-2-one ring, 5-thioxaimidazolidine- 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 ring (for example, 7,7a-dihydro-1H-pyrazolo [5,1-c] [1,2,4] triazole ring, 7, 7a-dihydro-1H -Pyrazolo [1,5-b] [1,2,4] triazole ring), pyrazolopyrimidine ring, imidazole ring (eg 4H-imidazole ring), imidazolopyrazole ring, pyrrole ring, isoxazolidinedione ring, thioxa Imidazolidinone ring (for example, 4-thioximidazolidin-2-one ring), imidazolidinedione ring (for example, hydantoin ring), imidazolidine dithione ring (for example, imidazolidine-2,4-dithione ring), thiazolidinedione ring , Pyrazoledione ring, indole ring and the like, and these may have the same group as the substituent represented by R1 described above at an arbitrary 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 R ₁ described above.

R represents a hydrogen atom or a substituent, and the substituent is the same as the substituent represented by R ₁ described above.

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

  Among the organic groups represented by A, an aryl group and a heterocyclic group are more preferable, and a heterocyclic group is more preferable, and more specifically, the following general formula (C-1) to The structure represented by (C-32) is mentioned, From the viewpoint of optical properties such as color tone, (C-1) to (C-15) are more preferable, and (C-1) to (C-) are more preferable. 10).

  In particular, (C-1), (C-9) and (C-10) are preferable from the viewpoint of spectral characteristics.

  In the general formulas (C-1) to (C-32), Ra to Rg are a hydrogen atom or a substituent, and each substituent may be the same or different. Examples include the same groups as the substituent represented by R1.

  Preferred examples of the substituent for Ra include an alkyl group, an aryl group, a heterocyclic group, a heteroaryl group, an acyl group, an acyloxy group, an amide group, a carbamoyl group, an amino group, and a cyano group, and more preferred are an alkyl group and an acyl group. , An amide group, a carbamoyl group, and an amino group.

  As the alkyl group, an alkyl group in which part or all of the alkyl group is substituted with a fluorine atom is also preferable. The alkyl group is more preferably a branched alkyl group (for example, isopropyl group, tert-butyl group, isobutyl group, sec-butyl group, neopentyl group, tert-amyl group, etc.).

  It is also preferred that at least one has a chelatable group.

  A chelatable group represents a substituent containing an atom having an unshared electron pair, specifically, a heterocyclic group, a hydroxyl group, a carbonyl group, an oxycarbonyl group, a carbamoyl group, an alkoxy group, a heterocyclic oxy group, Carbonyloxy group, urethane group, sulfonyloxy group, amino group, imino group, sulfonylamino group, sulfamoylamino group, acylamino group, ureido group, sulfonyl group, sulfamoyl group, alkylthio group, arylthio group, and heterocyclic thio group More preferably, hydroxy group, carbonyl group, oxycarbonyl group, carbamoyl group, alkoxy group, carbonyloxy group, urethane group, sulfonyloxy group, amino group, imino group, sulfonylamino group, acylamino group, ureido group Alkylthio group, arylthio group Group, and more preferably hydroxy group, a carbonyl group, a carbamoyl group, an alkoxy group, a sulfonylamino group, an acylamino group, and a heterocyclic group.

  Moreover, in General formula (1), l is an integer greater than or equal to 1, and is an integer represented by 1-3.

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

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

  Specifically, halogen ion, hydroxide ion, ammonia, pyridine, amine (such as methylamine, diethylamine, tributylamine, etc.), cyanide ion, cyanate ion, thiolate ion, thiocyanate ion, and bipyridines, aminopolycarboxylic acid Various chelate ligands such as acids, 8-hydroxyquinoline and the like can be mentioned, and the chelate ligands are exemplified in “Chelical Chemistry” by Keihei Ueno.

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

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

  Specific examples are shown below, but the present invention is not limited thereto. It should be noted that the structural formula shown here is only one of the limit structures among the possible resonance structures, and the distinction between a covalent bond (indicated by-) and a coordination bond (indicated by ...) is also formal. It does not represent an absolute distinction.

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

In the general formula (4), E ₁ , E ₂ and R ′ represent a substituent.

Specifically as a substituent, the thing similar to the substituent represented by said R < ₁ > can be mentioned. These substituents may be further substituted with the same substituent, or the substituents may be further bonded to each other to form a ring.

E ₁ and E ₂ are preferably electron-withdrawing groups, and as an index indicating the degree of electron-withdrawing properties, they are electron-withdrawing groups having a Hammett substituent constant (σp) of 0.1 or more and 0.9 or less. More preferably, E ₁ is preferably a Hammett substituent constant (σp) of 0.35 or more and 0.9 or less, and more preferably E ₁ and E ₂ both have a Hammett substituent constant (σp) of 0. It is 35 or more and 0.9 or less.

  A substituent having a Hammett's substituent constant (σp) of 0.1 or more and 0.9 or less indicating the degree of electron withdrawing will be described.

  As the value of Hammett's substituent constant σp here, Hansch, C .; It is preferable to use the values described in the report of Leo et al. (For example, J. Med. Chem. 16, 1207 (1973); ibid. 20, 304 (1977)).

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

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

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

Further, the van der Waals (VDW) volume of the substituent represented by E ₁ and E ₂ is preferably 75 3 or less, and more preferably 45 3 or less. In particular, E2 preferably has a van der Waals (VDW) volume of 35 to 3 or less.

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

Substituent Å3
Methyl group 25.4
Ethyl group 42.6
Isopropyl group 59.5
ter-butyl group 76.2
Phenyl group 74.9
Methoxy group 34.0
Amino group 22.2
Hydroxyl group 16.7
Chlorine atom 22.4
Bromine atom 26.5
Fluorine atom 13.3
Trifluoromethyl group 42.5
Preferable examples of the substituent represented by E ₁ and E ₂ include a halogenated alkyl group, a carbonyl group, a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, and an alkylsulfonyloxy group.

E ₁ is more preferably a halogen-substituted alkyl group or a cyano group, more preferably a halogen-substituted alkyl group, and most preferably a fluorine-substituted alkyl group.

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

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

  m and n each represent an integer of 0 to 2, and m + n ≧ 1.

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

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

  X represents a counter ion when a counter ion is required to neutralize the charge. For example, whether a compound is a cation, an anion, or has a net ionic charge depends on its metal, Depends on ligand and substituent. When the substituent has a dissociable group, it may be dissociated and have a negative charge. In this case, the charge of the whole molecule is neutralized by X.

  Typical cations are inorganic or organic ammonium ions (eg tetraalkylammonium ions, pyridinium ions), alkali metal ions and protons, whereas anions are specifically either inorganic or organic anions. For example, halogen anion (for example, fluoride ion, chloride ion, bromide ion, iodide ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion) ), Aryl disulfonate ions (for example, 1,3-benzenedisulfonate ions, 1,5-naphthalenedisulfonate ions, 2,6-naphthalenedisulfonate ions), alkyl sulfate ions (for example, methyl sulfate ions), sulfate ions , Thiocyanate ion , Perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion, enolate (acetylacetonate, hexafluoroacetylacetonate), hydroxide ion, sulfite ion, Examples thereof include nitrate ion, nitrite ion, carbonate ion, perchlorate ion, alkylcarboxylate ion, arylcarboxylate ion, tetraalkylborate, salicinate, benzoate, hexafluoroantimony and the like.

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

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

  The combination of chelate metal and squarylium is shown below.

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

  Moreover, the squarylium metal chelate compound of the present invention comprises a squarylium compound represented by the general formula (2) and a raw material (metal ion-containing compound) that gives a metal ion having coordination ability in a solvent at room temperature to 120 ° C. It is obtained by reacting at a temperature between 3 to 24 hours.

  In another preferred embodiment, the squarylium compound and the raw material providing the metal ion having coordination ability are pulverized into fine particles, or various dispersing machines (for example, a ball mill, a sand mill, an atomizer together with a polymer dispersant and a surfactant). A lighter, a roll mill, an agitator mill, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a jet mill, an ang mill, etc.) are preferably mixed while being dispersed in the form of fine particles because energy required for the reaction can be reduced.

  There is no limitation on the mixing ratio (molar ratio) between the metal ion-containing compound and the compound represented by the general formula (2). When squarylium compound: metal ion-containing compound = 1: Y, Y is preferably 0.1. Represents 100, more preferably 0.3 to 10, still more preferably 0.5 to 2.

  Examples of raw materials that give metal ions include bis (acetylacetonate) copper, copper acetate, copper bromide, copper nitrate, copper oxalate, copper sulfate, copper chloride, copper perchlorate, copper tetrafluoroborate, cyanide Copper iodide, copper iodide, copper trifluoromethanesulfonate, copper thiocyanate, nickel acetate, nickel sulfate, nickel (carbonate), nickel nitrate, nickel chloride, nickel bromide, nickel tetrafluoroborate, bis (acetylacetonate) Nickel, nickel perchlorate, zinc acetate, zinc bromide, zinc chloride, zinc nitrate, zinc tetrafluoroborate, zinc bis (acetylacetonate), cobalt nitrate, cobalt nitrite, cobalt acetate, bis (acetylacetonate) Cobalt, cobalt bromide, cobalt chloride, cobalt oxalate, cobalt thiocyanate and mono Such metal ion compounds having a ligand represented by the formula (3) is used.

General formula (3) M (X ₁ ) m (X ₂ ) l · Ws
In the formula, M represents a metal ion. X1 and X2 represents a ligand of independently 1 locus or bidentate, or different and are identical, X ₁ and X ₂ may be linked.

X ₁ and X ₂ are described in, for example, JP-A Nos. 2000-251957, 2000-31723, 2000-323191, 2001-6760, 2001-59062, and 2001-60467. Has been.

  At this time, from the viewpoint of improving solubility and compatibility with the binder, the raw material that gives metal ions preferably has an organic substance as a counter salt, and examples thereof include a diketonate compound and a general formula (3). Compounds.

  Although the typical example of a metal ion containing compound is given to the following, this invention is not limited to this.

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

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

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

  The squarylium metal chelate compound in the present invention refers to a squarylium metal chelate compound represented by the general formula (1) having at least one absorption maximum wavelength in the visible region (380 to 780 nm).

  Since the squarylium metal chelate compound of the present invention has good spectral characteristics, the extinction coefficient in a wavelength region shifted by about 200 nm from the absorption maximum wavelength is 1/100 to 1/1000 or less of the absorption coefficient of the absorption maximum. It is characterized by substantially no absorption in the wavelength range from the absorption maximum to the 100 nm long wave or short wave.

  As described above, the squarylium metal chelate compound in the present invention is characterized by having preferable spectral characteristics in the visible region.

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

[Synthesis Example 1]
<Synthesis of MD-32>

    D-90: 0.30 g is heated and dissolved in 25 ml of methanol, and nickel acetate (II) tetrahydrate: 0.13 g of a methanol solution: 10 ml is added dropwise thereto and reacted at 50 ° C. for 2 hours as it is. And the hue changed. The reaction solution was concentrated, and the recrystallized solid was collected by filtration and washed with water to obtain MD-32: 0.26 g.

  It identified by the MASS spectrum and elemental analysis, and confirmed that it was the target object. Moreover, when the MASS spectrum of the solution which dissolved D-90: 0.20g and nickel acetate (II) tetrahydrate in methanol was measured, the MASS spectrum which shows the production | generation of MD-32 was observed.

[Synthesis Example 2]
<Synthesis of MD-57>

  D-23: 0.33 g, copper (II) tetrafluoroacetylacetonate hydrate: 0.40 g was dissolved in methanol and heated to reflux for 1 hour. The solution was cooled and then concentrated under reduced pressure, and ethyl acetate and water were further added to extract the organic layer. A mixture obtained by concentrating the organic layer under reduced pressure was dissolved in methanol, and sodium perchlorate: 0.1 g was added little by little to precipitate a solid.

  This was collected by filtration to obtain MD-57: 0.28 g. It identified by the MASS spectrum and elemental analysis, and confirmed that it was the target object.

[Synthesis Example 3]
<Synthesis of MD-98>

  D-98: 0.56 g, MS-41 (using X-116 as the ligand): Acetone: 30 ml was added to 0.76 g, and the mixture was heated to reflux for 1 hour.

  The reaction solution was concentrated under reduced pressure to about 10 ml, to which 15 ml of acetonitrile was added and cooled to 5 ° C., and the precipitated crystals were filtered to obtain MD-98: 0.97 g. It identified by the MASS spectrum and elemental analysis, and confirmed that it was the target object.

  Moreover, when the MASS spectrum of the solution which melt | dissolved D-98: 0.30g and MS-41: 0.61g in methanol was measured, the MASS spectrum which shows the production | generation of MD-98 was observed.

  The composition for optical filters containing at least one squarylium metal chelate compound of the present invention is a composition with a dispersant (binder) for the purpose of film-forming stability in addition to the dye of the present invention, or further a solvent. Is used as a composition to which is added.

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

  The (meth) acrylate resin is synthesized by homopolymerizing or copolymerizing various methacrylate monomers or acrylate monomers, and by changing the monomer species and the monomer composition ratio, the desired (meth) acrylate is obtained. System resin can be obtained.

  In the present invention, it can be used together with a (meth) acrylate monomer and a copolymerizable monomer having an unsaturated double bond other than a (meth) acrylate monomer. Can also be used by mixing a plurality of other resins together with the poly (meth) acrylate resin.

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

  Polystyrene resins include homopolymers of styrene monomers, or random copolymers, block copolymers, and graft copolymers obtained by copolymerizing monomers with other unsaturated double bonds that can be copolymerized with styrene monomers. It is done. Furthermore, blends and polymer alloys obtained by blending such polymers with other polymers are also included.

  Examples of the styrene monomer include nuclear alkyl substitution such as styrene, α-methylstyrene, α-ethylstyrene, α-methylstyrene-p-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, etc. Examples of the halogenated styrene include styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene, and tribromostyrene. Styrene and α-methylstyrene are preferred.

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

《Optical filter and front filter for display》
The optical filter and the front filter for display of the present invention are composed of a composition comprising at least one dye of the present invention in a base material. Of course, it means that it is applied to the surface of the base material, or is sandwiched between the base material and the like.

  The optical filter according to the present invention is characterized by having at least one absorption maximum in the visible region, and is known as a so-called color filter, and is arranged in a square as a whole by arranging a large number of RGB three colors in a grid. It transmits light of a specific color like a component used in a solid-state imaging device such as a CCD image sensor or a color display using liquid crystal, and reduces light in a specific wavelength range without blocking the others. Or, it is used to block light and transmit other light. The display front filter of the present invention is preferably a plasma display panel front filter among display devices.

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

  For this reason, the display front filter of the present invention is characterized by having at least one absorption maximum in the visible region.

  In order to realize this, the dye of the present invention is characterized by having an absorption maximum in the visible region in a solution state, and more preferably has an absorption maximum at 450 to 620 nm for color tone adjustment, particularly neon emission. In order to cut, it is preferable to have an absorption maximum at 560 to 620 nm, and more preferable to have an absorption maximum at 580 to 600 nm.

  Examples of the substrate include a transparent resin plate, a transparent film, and transparent glass, and there is no particular limitation as long as the light transmittance at a wavelength of 400 to 700 nm is 40% or more.

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

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

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

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

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

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

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

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

  Examples of resins used include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins, polyvinyl alcohol resins, Examples thereof include polyvinyl modified resins (PVA, EVA, etc.) or resin monomers of those copolymer resins.

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

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

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

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

  The concentration of the composition varies depending on the gram extinction coefficient, coating thickness, target absorption intensity, target visible light transmittance, and the like, but is usually 0.1 ppm to 30% by mass with respect to the mass of the binder resin.

  Moreover, resin concentration is 1-50 mass% normally with respect to the whole coating material.

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

  Furthermore, it is preferable that the display front filter of the present invention has an electromagnetic wave shielding function and a near infrared ray blocking function.

  As the electromagnetic wave shield, a laminate using a silver thin film or a metal mesh mainly using copper can be used.

  As a laminate using a silver thin film, a laminate in which a dielectric such as indium oxide, zinc oxide, titanium oxide and silver are alternately laminated is preferable.

  As the metal mesh, a fiber mesh obtained by vapor-depositing a metal on a fiber, an etching mesh that forms a pattern using a photolithography technique and obtains a mesh by etching, or the like can be used.

  In addition, a method of patterning with a metal-containing ink, a method of applying silver halide, developing and fixing, and the like are also preferably used.

  As for the near-red ray blocking function, when an electromagnetic wave shield using a silver thin film is used, near-infrared rays can be simultaneously blocked due to scattering by silver free electrons.

  In addition, when a mesh, ink patterning, or development method is used, a film that absorbs or reflects near infrared rays is used separately.

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

  In addition, for UV protection, an ultraviolet cut acrylic plate may be used for the substrate, or an ultraviolet absorbing layer may be formed on one or both sides of the substrate, but the front film for display of the present invention absorbs UV. An agent may be included.

  Examples of ultraviolet absorbers include salicylic acid derivatives (UV-1), benzophenone derivatives (UV-2), benzotriazole derivatives (UV-3), acrylonitrile derivatives (UV-4), benzoic acid derivatives (UV-5), or organic There are metal complex salts (UV-6) and the like (UV-1) are phenyl salicylate, 4-t-tylphenylsalicylic acid, etc., and (UV-2) is 2-dihydroxybenzophenone, 2-hydroxy- 4-methoxybenzophenone and the like (UV-3) include 2- (2′-hydroxy-5′-methylphenyl) -benzotriazole, 2- (2′-hydroxy-3′-5′-di-butyl) Phenyl) -5-chlorobenzotriazole and the like (UV-4) is 2-ethylhexyl-2-cyano-3,3′-di Phenyl acrylate, methyl-α-cyano-β- (p-methoxyphenyl) acrylate and the like (UV-5) include resorcinol-monobenzoate, 2 ′, 4′-di-t-butylphenyl-3,5 -T-butyl-4-hydroxybenzoate and the like (UV-6) include nickel bis-octylphenylsulfamide, nickel salt of ethyl-3,5-di-t-butyl-4-hydroxybenzyl phosphate, etc. Can be mentioned.

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

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

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

  A plasma display panel display device is a device that displays a color image according to the following principle.

  A cell corresponding to each pixel (R (red), G (green), B (blue)) provided between two glass plates is provided between the front glass plate and the rear glass plate, and the cell Xenon gas or neon gas is sealed in the inside, and a phosphor corresponding to each pixel is applied to the back glass plate side in the cell.

  Due to the discharge between the display electrodes, the xenon gas and neon gas in the cell are excited to emit light, and ultraviolet rays are generated.

  By irradiating the phosphor with this ultraviolet ray, visible light corresponding to each pixel is generated.

  Then, an address electrode is provided on the rear glass plate, and by applying a signal to the address electrode, which discharge cell is displayed is controlled, and a color image is displayed.

  The front filter for display of the present invention can be suitably used as a neon cut filter that selectively blocks light emission of neon gas in the cell.

  As described above, the plasma display performs color display by phosphor emission, but when neon atoms are excited and return to the ground state, it is known to emit so-called neon orange light centered around 600 nm. (Journal of the Institute of Image Information and Television Engineers Vol. 51 No. 4P. 459-463 (1997)).

  For this reason, the plasma display has a disadvantage that a bright red color cannot be obtained due to a mixture of red and orange.

  In order to eliminate this drawback, it is preferable to cut off neon emission. When a neon emission absorption filter is prepared using the composition of the present invention, the dye of the present invention has an absorption maximum at 560 to 620 nm in a solution state. Preferably, it has an absorption maximum at 580 to 605 nm.

  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 is given and this invention is demonstrated concretely, the embodiment of this invention is not limited to these.

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

(Optical filter 1B)
A 0.3% dimethoxyethane solution of the squarylium metal chelate dye MD-2 of the present invention and an acrylic resin (Olivein BPS5896: manufactured by Toyo Ink Manufacturing Co., Ltd.) are mixed at a ratio of 1:15, and a film made of polyethylene terephthalate (PET) An optical filter (Sample 1B) was prepared by coating with a bar coater on (thickness: 100 μm) and drying. This filter was light blue and was found to absorb visible light effectively.

(Preparation of optical filters 2A-18A, 2B-18B and comparative optical filters 19A, 20A, 19B, 20B)
Optical filters for comparison with the optical filter of the present invention were prepared in the same manner except that the dyes shown in Tables 5 and 6 below were used instead of the squarylium metal chelate dyes MD-1 and MD-2.

  The light resistance and environmental preservation of the obtained optical filter were evaluated by the following methods. The results are shown in Table 5 and Table 6 together.

《Light resistance》
% Decrease in transmission spectral density at the maximum absorption wavelength in the visible region from an unexposed sample of the filter after exposure to xenon light (70000 lux) for 50 hours using a xenon weather meter manufactured by Suga Test Instruments Co., Ltd. Rate%) was calculated and evaluated according to the following criteria. Practically, it is desirable that it is more than ○.
(Dye remaining rate%) = (exposed sample maximum absorption wavelength concentration / unexposed sample maximum absorption wavelength concentration) × 100, and was evaluated in five stages based on the following evaluation criteria. It is preferable that it is above.

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

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

  A: The filter is not devitrified, cracked or cracked before and after storage.

  B: Some devitrification is observed after storage, but there is no practical problem.

  C: Obvious devitrification was observed.

  D: A crack or crack was observed.

(Optical filter C)
The squarylium metal chelate dye MD-96 of the present invention is 20% methyl ethyl ketone of polystyrene resin (St / HEMA / SMA = 30/40/30 copolymer, St: styrene, HEMA: 2-hydroxyethyl methacrylate, SMA: stearyl methacrylate). / Toluene mixed solution (methyl ethyl ketone: toluene = 9: 1) was mixed at a ratio of 0.03%, coated on a glass substrate with a bar coater, and dried to prepare an optical filter (sample C). This filter had a bluish purple color and was found to absorb visible light effectively even with a composition in which the binder was changed to polystyrene resin.

(Optical filter D)
Using the squarylium metal chelate dye MD-86 of the present invention, an optical filter (sample D) was prepared in the same manner as the optical filter 1A except that the polyester resin was changed to a polyvinyl chloride resin. This filter had a bluish purple color, and it was found that even a composition with a changed binder effectively absorbs visible light.

(Optical filter E)
A 0.5% tetrahydrofuran solution of the squarylium metal chelate dye MD-55 of the present invention and a 20% dimethoxyethane solution of hot-melt polyester resin (Diabond Kogyo Co., Ltd., trade name: SP3300X1) are mixed at a ratio of 2: 8. The polyester film for peeling (Toyobo Co., Ltd., trade name: MRF75, thickness 75 μm) is coated with a bar coater and dried, and then the polyester film (Toyobo Co., Ltd., trade name: A4300, thickness 100 μm) is heated on the coated surface. Attaching using a roll laminating apparatus, peeling off the peeling polyester film, making the SP3300X1 coated surface glass side, applying heat to the glass substrate for 1 minute with an iron having a surface of about 100 ° C., and attaching an optical filter (sample E ) Was produced. This filter had a blue color, and it was found that even a composition with a changed binder effectively absorbs visible light.

《Front filter for display》
(Preparation of front filter 1 for diffi-sui)
To a polyethylene terephthalate (PET) film (thickness 100 μm), 0.5 g of a 0.2% tetrahydrofuran solution of the squarylium metal chelate dye (MD-50) of the present invention and 6.5 g of a 20% methyl ethyl ketone / toluene mixed solution of a polyester resin were added. After mixing, coating with a bar coater and drying were performed to obtain a coating film having a thickness of 5 μm.

  The transmittance curve of the front filter for display has a minimum value at 610 nm, there is no other clear minimum value, and the wavelength of the minimum value of visible light transmittance is a wavelength region of 560 to neon light emission. Since it is at 620 nm, 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.

  Using a xenon fade meter (70,000 Lux), when the xenon light was exposed for 48 hours from the opposite side of the dye-coated surface, the dye residual percentage at the visible region maximum absorption wavelength from the unexposed sample was calculated to be 94. .5%.

  Further, the residual ratio of the dye after exposure for 10 days was 78.4%, and it was possible to provide a neon light-emitting cut filter and a display front filter with good light resistance.

(Preparation of front filter 2 for display)
A PET film (thickness: 100 μm) was mixed with 0.4 g of a 0.5% dichloroethane solution of the squarylium metal chelate dye (MD-91) of the present invention and 5.0 g of a 35% dimethoxyethane solution of an acrylic resin, and then a bar coater. And dried to obtain a coating film having a thickness of 5 μm.

  The transmittance curve of this front filter for display has a minimum value at 589 nm, there is no clear minimum value other than this, and the wavelength of the minimum value of visible light transmittance is a wavelength range of 560 to neon light emission. Since it is at 620 nm, 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.

  Using a xenon fade meter (70,000 Lux), when the xenon light was exposed for 48 hours from the opposite side of the dye-coated surface, the dye residual% at the visible region maximum absorption wavelength from the unexposed sample was calculated. 2%.

  Further, the residual ratio of the dye after exposure for 10 days was 58.3%, and it was possible to provide a neon light-emitting cut filter and a display front filter with good light resistance.

(Preparation of front filter 3 for display)
An ultraviolet absorbing coating solution (Sumitomo Osaka Cement Co., Ltd.) containing an isocyanate resin as a binder and zinc oxide as an ultraviolet absorber on a PET resin on the opposite side of the dye-containing layer surface of the display front filter 1 is a bar coater. And dried 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.

  Using a xenon fade meter (70,000 Lux), when the xenon light was exposed for 10 days from the surface of the ultraviolet absorbing layer, the dye residual ratio% at the maximum absorption wavelength in the visible region from the unexposed sample was calculated. Thus, it was possible to provide a neon light emission cut filter having an ultraviolet absorption layer and a front filter for display having excellent light resistance.

(Preparation of front filter 4 for display)
A near-infrared absorbing dye (N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium is formed on the PET resin surface opposite to the dye-containing layer surface of the display front filter 1. 0.5 g of cyclohexanone solution of 5% cyclohexanone and 3 g of polyester resin 20% cyclohexanone solution were mixed, coated with a bar coater and dried to obtain a coating film having a film thickness of 6 μm. . The front filter for display was measured with a Hitachi spectrophotometer (U-3500). The wavelengths at the minimum transmittance were 601 nm and 1100 nm.

  Using a xenon fade meter (70,000 Lux), when the xenon light was exposed from the near-infrared absorbing layer surface for 10 days, the percent residual dye at the visible region maximum absorption wavelength from the unexposed sample was calculated. % Neon light emission cut filter having a near infrared absorption layer and a front filter for display.

(Preparation of front filter 5 for display)
0.5 g cyclohexanone solution of the above near infrared absorbing dye (N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium hexafluoroantimonate) And 0.5 g of a 0.5% tetrahydrofuran solution of the squarylium metal chelate dye (MD-98) of the present invention is mixed with 6.5 g of a 20% tetrahydrofuran solution of a polyester resin, and applied to a PET film (thickness 100 μm) with a bar coater. The coating film having a film thickness of 5 μm was obtained by drying. The front filter for display was measured with a Hitachi spectrophotometer (U-3500).

  The wavelengths at the minimum value of the transmittance were 590 nm and 1100 nm.

  Further, 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole is absorbed on the PET resin surface opposite to the near-infrared absorbing dye and the squarylium metal chelate dye-containing surface of the present invention. The ultraviolet absorbing coating solution contained as an agent 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 (70,000 Lux), when the xenon light was exposed for 48 hours from the surface of the ultraviolet absorption layer, the dye residual rate% at the maximum absorption wavelength in the visible region from the unexposed sample was calculated. The residual ratio of the dye after exposure for 10 days is 72.7%, and the squarylium metal chelate dye of the present invention has excellent light resistance even when used in the same layer as the near infrared absorbing dye. We were able to provide a front filter.

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

(Comparative example)
(Preparation of front filter 1 for comparison display)
A comparative display front filter 1 was prepared in the same manner as the above-described display front filter 1 except that the squarylium compound D-4 was used instead of the squarylium metal chelate dye MD-99 of the present invention.

  The dye residual rate% after exposure to xenon light from the ultraviolet absorbing layer surface for 48 hours using a xenon fade meter (70,000 Lux) was 47.6%, and the dye residual rate after exposure for 10 days was 14.2%. Met. From the above, the comparative display front filter 1 is significantly inferior in light resistance to the display front filter 1 of the present invention, and the display front filter using the squarylium metal chelate-containing composition of the present invention is light resistant. It turns out that it is very excellent.

(Preparation of front filter 2 for comparison display)
A comparative display front filter 2 was produced in the same manner as the display front filter 5 except that the squarylium compound D-68 was used instead of the squarylium metal chelate dye MD-98 of the present invention.

  The dye residual rate% after exposure to xenon light for 48 hours from the ultraviolet absorbing layer surface using a xenon fade meter (70,000 Lux) was 53.1%, and the dye residual rate after 10 days exposure was 16.8%. Met. The comparative display front filter 2 is significantly inferior in light resistance to the display front filter 5 of the present invention, and the display front filter using the squarylium metal chelate-containing composition of the present invention is extremely excellent in light resistance. You can see that

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

Claims (5)

The composition for optical filters characterized by containing the squarylium metal chelate pigment | dye represented by following General formula (1).
General formula (1)
M [(SQ) l (W ₁ ) m (W ₂ ) n] X
(In the formula, M represents a metal ion. SQ represents a squarylium compound represented by the following general formula (2), W ₁ and W ₂ each independently represent a monodentate or bidentate ligand, and 1 is an integer of 1 or more, m and n each represents an integer of 0 to 2, l + m + n ≧ 2, and X is a counter ion necessary for neutralizing the charge Represents.)

(In the formula, A represents an arbitrary organic group, B ₁ , B ₂ , B ₃ and B ₄ are carbon atoms or nitrogen atoms. When they are carbon atoms, they have a hydrogen atom or a substituent, and have an aromatic ring. Form.
R ₁ represents a hydrogen atom or a substituent. ) The composition for an optical filter according to claim 1, wherein the metal ion is at least one metal ion selected from cobalt, nickel, copper, and zinc. An optical filter comprising the optical filter composition according to claim 1. The front filter for a display, wherein the optical filter according to claim 3 is a front filter for a display. 5. The display front filter according to claim 4, wherein the display front filter is a plasma display front filter, and the dye represented by the following general formula (1) has an absorption maximum in a range of 560 to 620 nm. filter.
General formula (1)
M [(SQ) l (W ₁ ) m (W ₂ ) n] X
(In the formula, M represents a metal ion. SQ represents a squarylium compound represented by the following general formula (2), W ₁ and W ₂ each independently represent a monodentate or bidentate ligand, and 1 is an integer of 1 or more, m and n each represents an integer of 0 to 2, l + m + n ≧ 2, and X is a counter ion necessary for neutralizing the charge Represents.)

(In the formula, A represents an arbitrary organic group, B ₁ , B ₂ , B ₃ and B ₄ are carbon atoms or nitrogen atoms. When they are carbon atoms, they have a hydrogen atom or a substituent, and have an aromatic ring. Form.
R ₁ represents a hydrogen atom or a substituent. )