JP2007256717A - Optical filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical filter which is especially suitable for an optical filter for an image display device having a sharp light absorption particularly in a wavelength region of 450 to 620 nm. <P>SOLUTION: The optical filter contains at least one kind of cyanin compound expressed by the formula (I). In the formula (I), R<SP>1</SP>to R<SP>4</SP>present respectively independently hydrogen atom, alkyl group having the number of carbon atoms 1 to 8, allyl group having the number of carbon atoms 6 to 20 or allyl-alkyl group having the number of carbon atoms 7 to 20 and R<SP>1</SP>to R<SP>4</SP>may be respectively connected to form a ring. Y<SP>1</SP>and Y<SP>2</SP>present respectively independently alkyl group having the number of carbon atoms 1 to 8, allyl group having the number of carbon atoms 6 to 20 or allyl-alkyl group having the number of carbon atoms 7 to 20, and R<SP>5</SP>and R<SP>6</SP>present respectively independently perhaloalkyl group having the number of carbon atoms 1 to 8. The alkyl group having the number of carbon atoms 1 to 8, the allyl group having the number of carbon atoms 6 to 20 and the allyl-alkyl group having the number of carbon atoms 7 to 20 presented by R<SP>1</SP>to R<SP>4</SP>, Y<SP>1</SP>and Y<SP>2</SP>may have substituents, and a methylene group in the alkyl group having the number of carbon atoms 1 to 8 may be substituted with -O- or -CH=CH-. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an optical filter containing a cyanine compound having a specific molecular structure. The cyanine compound is particularly useful as a light absorber to be contained in an optical filter for an image display device.

  A compound having a strong absorption in the wavelength range of 450 nm to 700 nm, particularly a compound having a maximum absorption (λmax) in the range of 450 to 620 nm, an optical recording layer of an optical recording medium such as DVD ± R, or a liquid crystal display (LCD) It is used as an optical element in an optical filter for an image display device such as a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display (CRT), a fluorescent display tube, or a field emission display.

  For example, as an application of the optical element in the image display device, there is a light absorber for a color filter. The image display device displays a color image with a combination of light of the three primary colors of red, blue, and green, but the light for displaying the color image has a decrease in display quality such as 550 to 620 nm between green and red. In addition, light that causes malfunction of an infrared remote controller of 750 to 1100 nm is also included. The optical filter is required to have a function of selectively absorbing light of the above-described unnecessary wavelength, and at the same time, in order to prevent reflection and reflection of external light from a fluorescent lamp or the like, 480 to 500 nm and 540 to 560 nm. It is also necessary to absorb light of the wavelength. Therefore, an optical filter containing a light-absorbing compound (light absorber) that selectively absorbs light of these wavelengths is used in an image display device or the like.

  Further, in recent years, a light absorber that selectively absorbs a wavelength of 450 to 620 nm has been demanded in order to ensure sufficient color purity and color separation of the display element and to improve image quality. These light absorbers are required to have particularly steep light absorption, that is, having a small half-value width of λmax and not to lose its function due to light, heat, or the like.

  As an optical filter containing a light absorber, for example, the following Patent Document 1 discloses an optical filter using an azaporphyrin compound having a maximum absorption wavelength at 570 to 605 nm. An optical filter using a condensed polycyclic pigment having a maximum absorption wavelength at ˜600 nm is disclosed. Patent Document 3 below discloses an optical filter using a dipyrromethene metal chelate compound having a maximum absorption wavelength at 440 to 510 nm. It is disclosed. However, the compounds used in these optical filters do not have satisfactory performance in terms of absorption wavelength characteristics or affinity with solvents and binder resins.

  Further, Patent Document 4 below discloses an organic soluble cationic dye having a fluorinated alkylsulfonyl counter ion, but does not describe or suggest that the cationic dye can be used in an optical filter.

JP 2003-57437 A JP 2004-310072 A JP 2003-57436 A JP-A-8-253705

  Accordingly, an object of the present invention is to provide an optical filter that has steep light absorption particularly in a wavelength region of 450 to 620 nm and is particularly suitable for an image display apparatus.

  As a result of various studies, the present inventors have found that a cyanine compound having a specific molecular structure has high solubility in an organic solvent and has steep light absorption in a specific wavelength region. It was found that the image characteristics can be remarkably improved.

  The present invention has been made based on the above findings, and has achieved the above object by providing an optical filter comprising at least one cyanine compound represented by the following general formula (I): It is.

（式中、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は、それぞれ独立に、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、Ｒ¹とＲ²、及びＲ³とＲ⁴は、それぞれ連結して環を形成していてもよい。Ｙ¹及びＹ²は、それぞれ独立に、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、Ｒ⁵及びＲ⁶は、それぞれ独立に、炭素原子数１〜８のパーハロアルキル基を表す。Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｙ¹及びＹ²で表される上記炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基及び炭素原子数７〜２０のアリールアルキル基は、置換基を有していてもよく、上記炭素原子数１〜８のアルキル基中のメチレン基は、−Ｏ−又は−ＣＨ＝ＣＨ−で置き換えられていてもよい。）

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. R ¹ and R ² , and R ³ and R ⁴ may be linked to each other to form a ring, and Y ¹ and Y ² each independently represent 1 to 1 carbon atoms. 8 represents an alkyl group, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, and R ⁵ and R ⁶ each independently represents a perhaloalkyl group having 1 to 8 carbon atoms. R ¹ , R ² , R ³ , R ⁴ , Y ¹ and Y ² represented by the above alkyl group having 1 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms and 7 to 20 carbon atoms The arylalkyl group may have a substituent, and the above alkyl group having 1 to 8 carbon atoms. (The methylene group in it may be replaced by —O— or —CH═CH—.)

  Moreover, this invention achieves the said objective by providing the optical filter characterized by including the cyanine compound represented by the following general formula (II) at least 1 type.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｙ¹及びＹ²は、上記一般式（Ｉ）と同じであり、Ｘ¹及びＸ²は、それぞれ独立に、ＣＦ₃−又はＣＦ₃Ｏ−を表す。）

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Y ¹ and Y ² are the same as those in the general formula (I), and X ¹ and X ² are each independently , CF ₃ — or CF ₃ O—.

  Moreover, this invention achieves the said objective by providing the optical filter characterized by including the cyanine compound represented by the following general formula (III) at least 1 type.

（式中、Ｒ¹、Ｒ²、Ｒ⁵、Ｒ⁶、Ｙ¹及びＹ²は、上記一般式（Ｉ）と同じであり、Ａは、置換基を有していてもよいベンゼン環又はナフタレン環を表す。）

Wherein R ¹ , R ² , R ⁵ , R ⁶ , Y ¹ and Y ² are the same as those in the general formula (I), and A is a benzene ring or naphthalene which may have a substituent. Represents a ring.)

  The cyanine compound contained in the optical filter of the present invention has high solubility in an organic solvent and is excellent in the stability of the coating solution. In addition, steep light absorption is exhibited at 450 to 700 nm, particularly 480 to 600 nm. Therefore, the optical filter of the present invention containing the cyanine compound is an optical filter suitable for image display applications, particularly plasma display applications.

  Hereinafter, preferred embodiments of the optical filter of the present invention will be described in detail.

First, the cyanine compound represented by the general formula (I) will be described.
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , Y ¹ and Y ² in the general formula (I) include methyl, ethyl, propyl, isopropyl, butyl, butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tert-heptyl, n- octyl, isooctyl, tert-octyl, 2-ethylhexyl, and the like, R ¹ Examples of the aryl group having 6 to 20 carbon atoms represented by R ² , R ³ , R ⁴ , Y ¹ and Y ² include phenyl, naphthyl, anthracen-1-yl, phenanthren-1-yl and the like. as the ^{R 1, R 2, R 3} , R 4, Y 1 and arylalkyl group having a carbon number of 7 to 20 represented by Y ^2, benzyl, phenethyl, 2-phenylpropane, di Enirumechiru, triphenylmethyl, a styryl, cinnamyl, and the like.

The perhaloalkyl group having 1 to 8 carbon atoms represented by R ⁵ and R ⁶ in the general formula (I) is R ¹ , R ² , R ³ , R ⁴ , Y ¹ in the general formula (I). And an alkyl group having 1 to 8 carbon atoms exemplified as the alkyl group having 1 to 8 carbon atoms represented by Y ² and a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom is preferable because the solubility of the resulting cyanine compound is improved.
Specific examples of the perfluoroalkyl group substituted with a fluorine atom include trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, Examples include pentafluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, and the like, and a trifluoromethyl group is particularly preferable.

An alkyl group having 1 to 8 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , Y ¹ and Y ² ; represented by R ¹ , R ² , R ³ , R ⁴ , Y ¹ and Y ² An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , Y ¹ and Y ² , and R ⁵ and R ⁶ Any of the represented perhaloalkyl groups having 1 to 8 carbon atoms may have a substituent. Examples of the substituent include the following. Incidentally, R ¹ to R ⁶ and Y ¹ and Y ² is a group containing carbon atoms such as an alkyl group having 1 to 8 carbon atoms described above, and their groups, among the following substituents In the case of having a substituent containing a carbon atom, the number of carbon atoms of R ^{1 to} R ⁶ and the total of Y ¹ and Y ² including the substituent satisfies the specified range.
Examples of the substituent include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, and 3-hexyl. Alkyl groups such as cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl Methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, hex Alkoxy groups such as tiloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy; methylthio, ethylthio, propylthio, isopropylthio, butylthio, Dibutylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tert-amylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio, 2-ethylhexylthio, etc. Alkylthio group; vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl , Alkenyl groups such as 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, tricosenyl; arylalkyls such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl Groups; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; arylthio groups such as phenylthio and naphthylthio; Benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, Benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxy Heterocyclic groups such as oxazolidin-3-yl; halogen atoms such as fluorine, chlorine, bromine, iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoro Acyl groups such as methylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; acetyloxy, benzoylo Acyloxy groups such as bis; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino , Methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbo Substituted amino groups such as ruamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl Group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group and the like, and these groups may be further substituted. Moreover, the carboxyl group and the sulfo group may form a salt.

As the cyanine compound according to the present invention represented by the above general formula (I), in the above general formula (I), R ¹ , R ² , R ³ and R ⁴ are alkyl groups having 1 to 8 carbon atoms. Some, R ⁵ and R ⁶ are perfluoroalkyl groups having 1 to 8 carbon atoms, and Y ¹ and Y ² are alkyl groups having 1 to 8 carbon atoms or 7 to 20 carbon atoms. An arylalkyl group is preferred because it is highly soluble in organic solvents and can be synthesized at low cost.

As the cyanine compound according to the present invention represented by the general formula (II), in the general formula (II), R ¹ , R ² , R ³ and R ⁴ are alkyl groups having 1 to 8 carbon atoms. Some, R ⁵ and R ⁶ are perfluoroalkyl groups having 1 to 8 carbon atoms, and Y ¹ and Y ² are alkyl groups having 1 to 8 carbon atoms, with respect to the organic solvent. It is preferable because it is highly soluble and can be synthesized at low cost.

As the cyanine compound according to the present invention represented by the general formula (III), in the general formula (III), R ¹ and R ² are alkyl groups having 1 to 8 carbon atoms, R ⁵ and R ⁶ is a perfluoroalkyl group having 1 to 8 carbon atoms, and Y ¹ and Y ² are alkyl groups having 1 to 8 carbon atoms, which are highly soluble in organic solvents and inexpensive. It is preferable because it can be synthesized.

  In the optical filter of the present invention, the cyanine compounds represented by any one of the above general formulas (I) to (III) can be used singly or in combination.

  Preferable specific examples of the cyanine compound according to the present invention represented by the above general formulas (I) to (III) include the following compound Nos. 1-24 are mentioned. In the cyanine compound according to the present invention, the polymethine chain may have a resonance structure, and the cation may be on the nitrogen atom in the other heterocyclic skeleton.

  A diimonium compound can be used in combination with the optical filter of the present invention as necessary. As the dimonium compound, a known compound that is usually used as a near-infrared absorbing compound in an optical filter can be used. However, a coating solution using a dimonium compound having the same anion as the cyanine compound according to the present invention is used. This is preferable because of the increased stability.

  As said dimonium compound, the compound represented by the following general formula (IV) can be used preferably.

（式中、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³及びＲ¹⁴は、それぞれ独立に、水素原子又は炭素原子数１〜８のアルキル基を表し、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜８のアルキル基又はアミノ基を表す。Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸で表される炭素原子数１〜８のアルキル基、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸で表されるアミノ基は、置換基を有していてもよい。上記炭素原子数１〜８のアルキル基中のメチレン基は、−Ｏ−又は−ＣＨ＝ＣＨ−で置換されていてもよく、ｒは１〜４の数を表し、Ｒ⁵及びＲ⁶は、上記一般式（Ｉ）と同じである。）

(Wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an amino group, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ^11. R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , an alkyl group having 1 to 8 carbon atoms, represented by R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ The amino group may have a substituent, and the methylene group in the alkyl group having 1 to 8 carbon atoms may be substituted with —O— or —CH═CH—, and r is 1 It represents the number of to 4, R ⁵ and R ⁶ are as defined for general formula (I).)

In the optical filter of the present invention, the content of the cyanine compound represented by any one of the above general formulas (I) to (III) is usually 1 to 1000 mg / m ² , preferably 5 to 5 per unit area of the optical filter. was 100 mg / m ^2, the content is less than 1 mg / m ^2, can not be sufficiently exhibited a light absorption effect, when the content exceeds 1000 mg / m ^2, the color filter is strongly There is a possibility that the display quality and the like are deteriorated too much, and further, there is a possibility that the brightness is lowered due to an increase in the blending amount of the light absorber.

The content of the diimmonium compound in combination as needed, 10~10000mg / m ² per unit area of the optical filter, preferably 50 to 1000 mg / m ^2.

  The optical filter of the present invention contains at least one cyanine compound represented by any one of the above general formulas (I) to (III). Since the cyanine compound has an absorption maximum wavelength in the range of 450 to 620 nm or in the vicinity thereof and can selectively absorb and block a part of visible light, the optical component of the present invention containing the cyanine compound can be used. The filter is particularly suitable as an optical filter for an image display device used for improving the quality of a display image. The optical filter of the present invention is for an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode tube display device (CRT), a fluorescent display tube, and a field emission display. In addition, it can be used for various applications such as spectacle lenses, windows, analyzer applications, semiconductor device applications, astronomical observation applications, and optical communication applications.

The optical filter of the present invention is usually disposed in front of the display. For example, the optical filter of the present invention may be directly attached to the surface of the display. When a front plate is provided in front of the display, the optical filter is attached to the front side (outside) or the back side (display side) of the front plate. May be.

  Although the shape of the optical filter of the present invention is not particularly limited, each layer such as an undercoat layer, an antireflection layer, a hard coat layer, a lubricating layer, and a protective layer is usually provided on the transparent support as necessary. The thing of the provided multilayer structure is mentioned. Examples of the method of incorporating the optional components of the cyanine compound according to the present invention, a light absorber that is a dye compound other than the cyanine compound according to the present invention, and various stabilizers into the optical filter of the present invention include (2) A transparent support or a method of coating each arbitrary layer, (3) An adhesive layer between any two adjacent members selected from the transparent support and any arbitrary layer (4) A method of providing a light-absorbing layer containing a light-absorbing agent such as a cyanine compound according to the present invention separately from any arbitrary layer.

  Examples of the material for the transparent support include inorganic materials such as glass; cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; polyamides; polycarbonates; polyethylenes Polyester such as terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene Polyolefins such as polypropylene and polymethylpentene; Acrylic resins such as polymethyl methacrylate; Polycarbonate; Polysulfone Polyethersulfone; polyetherketone; polyetherimide; polymer materials such as polyoxyethylene and norbornene resin. The transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze is preferably 2% or less, and more preferably 1% or less. The refractive index is preferably 1.45 to 1.70.

  In the transparent support, in addition to the cyanine compound according to the present invention, other light absorbers, infrared absorbers, ultraviolet absorbers, phenol-based, phosphorus-based, sulfur-based antioxidants, flame retardants, lubricants, electrification An inhibitor, inorganic fine particles, light resistance imparting agent, aromatic nitroso compound, aminium compound, iminium compound, transition metal chelate compound and the like can be added, and the transparent support is subjected to various surface treatments. You can also.

  As the light absorber other than the cyanine compound according to the present invention, for example, when an optical filter is used for an image display device, the light absorber for adjusting the color tone, the light absorption for preventing reflection of external light and reflection. In the case where the image display device is a plasma display, a light absorber for preventing infrared remote control malfunction is used.

  As the light absorber for color tone adjustment, trimethine indolium compound, trimethine benzoxazolium compound, trimethine benzothiazolium compound are used for removing orange light having a wavelength of 450 to 620 nm. Trimethine cyanine derivatives such as pentamethine oxazolium compounds, pentamethine cyanine derivatives such as pentamethine thiazolium compounds, squarylium dye derivatives, azomethine dye derivatives, xanthene dye derivatives, azo dye derivatives, oxonol dye derivatives, benzylidene dye derivatives A pyromethene dye derivative; an azo metal complex derivative: a rhodamine dye derivative; a phthalocyanine derivative; a porphyrin derivative; a dipyrromethene metal chelate compound.

  Examples of the light absorbing agent for reflection or reflection of outside light (corresponding to a wavelength of 480 to 500 nm) include trimethine indolium compound, trimethine oxazolium compound, trimethine thiazolium compound, indolidene trimethine thiazonium. Trimethine cyanine derivatives such as compounds; phthalocyanine derivatives; naphthalocyanine derivatives; porphyrin derivatives; dipyrromethene metal chelate compounds.

  Examples of the above-mentioned light absorber for preventing infrared remote control malfunction (corresponding to a wavelength of 750 to 1100 nm) include diimonium compounds other than the compound represented by the general formula (IV); pentamethine benzoindolium compound, pentamethine benzoxa Pentamethine cyanine derivatives such as zolium compounds and pentamethine benzothiazolium compounds; heptamethine indolium compounds, heptamethine benzoindolium compounds, heptamethine oxazolium compounds, heptamethine benzoxazolium compounds, heptamethine thiazo Heptamethine cyanine derivatives such as lium compounds and heptamethine benzothiazolium compounds; squarylium derivatives; bis (stilbenedithiolato) compounds, bis (benzenedithiolato) nickel compounds, bis (camphagethiolato) nickel Squarylium derivatives; nickel complexes of compounds such as azo dye derivatives; phthalocyanine derivatives; porphyrin derivatives; dipyrromethene metal chelate compounds, and the like.

In the optical filter of the present invention, the above light absorber for color tone adjustment, a light absorber for preventing reflection of external light and reflection, and a light absorber for preventing infrared remote control malfunction (near infrared absorber) are: The layer containing the cyanine compound according to the present invention may be contained in the same layer or may be contained in another layer. Their usage, respectively, generally in the range of per unit area 1 to 1000 mg / m ² of the optical filter, preferably 5 to 100 mg / m ^2.

  Examples of the inorganic fine particles that can be added to the transparent support include silicon dioxide, titanium dioxide, barium sulfate, calcium carbonate, talc, and kaolin.

  Examples of the various surface treatments that can be applied to the transparent support include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser. Treatment, mixed acid treatment, ozone oxidation treatment and the like.

  The said undercoat which can be provided in the optical filter of this invention is a layer used between a transparent support body and an optical filter layer, when providing the filter layer containing a light absorber separately from arbitrary each layer. The undercoat layer is formed as a layer containing a polymer having a glass transition temperature of −60 to 60 ° C., a layer having a rough surface on the filter layer side, or a layer containing a polymer having affinity with the polymer of the filter layer. In addition, the undercoat layer is provided on the surface of the transparent support on which the filter layer is not provided, and improves the adhesion between the transparent support and a layer (for example, an antireflection layer or a hard coat layer) provided thereon. It may be provided for improving the affinity between the optical filter and the adhesive for bonding the optical filter and the image display device. The thickness of the undercoat layer is preferably 2 nm to 20 μm, more preferably 5 nm to 5 μm, further preferably 20 nm to 2 μm, still more preferably 50 nm to 1 μm, and most preferably 80 nm to 300 nm. The undercoat layer containing a polymer having a glass transition temperature of −60 to 60 ° C. adheres the transparent support and the filter layer due to the tackiness of the polymer. Polymers having a glass transition temperature of −60 to 60 ° C. are exemplified by polymerization of vinyl chloride, vinylidene chloride, vinyl acetate, butadiene, neoprene, styrene, chloroprene, acrylic ester, methacrylic ester, acrylonitrile or methyl vinyl ether, or a copolymer thereof. It can be obtained by polymerization. The glass transition temperature is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, further preferably 30 ° C. or lower, further preferably 25 ° C. or lower, and further preferably 20 ° C. or lower. Most preferred. The elastic modulus at 25 ° C. of the undercoat layer is preferably 1 to 1000 MPa, more preferably 5 to 800 MPa, and most preferably 10 to 500 MPa. The undercoat layer whose surface is a rough surface forms a filter layer on the rough surface, thereby bonding the transparent support and the filter layer. An undercoat layer having a rough filter layer surface can be easily formed by applying a polymer latex. The average particle size of the latex is preferably 0.02 to 3 μm, and more preferably 0.05 to 1 μm. Examples of the polymer having affinity with the binder polymer of the filter layer include acrylic resin, cellulose derivative, alginic acid, gelatin, casein, starch, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, soluble nylon, and polymer latex. The optical filter of the present invention may be provided with two or more undercoat layers. In the undercoat layer, a solvent for swelling the transparent support, a matting agent, a surfactant, an antistatic agent, a coating aid, a hardening agent, and the like may be added.

  In the antireflection layer that can be provided in the optical filter of the present invention, a low refractive index layer is essential. The refractive index of the low refractive index layer is lower than the refractive index of the transparent support. The refractive index of the low refractive index layer is preferably 1.20 to 1.55, and more preferably 1.30 to 1.50. The thickness of the low refractive index layer is preferably 50 to 400 nm, and more preferably 50 to 200 nm. The low refractive index layer is a layer made of a fluorine-containing polymer having a low refractive index (Japanese Patent Laid-Open Nos. 57-34526, 3-130103, 6-115023, 8-313702, and 7- 168004), a layer obtained by a sol-gel method (described in JP-A-5-208811, JP-A-6-299091, and JP-A-7-168003), or a layer containing fine particles (Japanese Patent Publication No. 60). -59250, JP-A-5-13021, JP-A-6-56478, JP-A-7-92306, and JP-A-9-288201). In the layer containing fine particles, voids can be formed in the low refractive index layer as microvoids between the fine particles or within the fine particles. The layer containing fine particles preferably has a porosity of 3 to 50% by volume, and more preferably has a porosity of 5 to 35% by volume.

  In order to prevent reflection in a wide wavelength region, in the antireflection layer, in addition to the low refractive index layer, a layer having a high refractive index (medium / high refractive index layer) is preferably laminated. The refractive index of the high refractive index layer is preferably 1.65 to 2.40, and more preferably 1.70 to 2.20. The refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably 1.50 to 1.90, and more preferably 1.55 to 1.70. The thickness of the middle / high refractive index layer is preferably 5 nm to 100 μm, more preferably 10 nm to 10 μm, and most preferably 30 nm to 1 μm. The haze of the middle / high refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The middle / high refractive index layer can be formed using a polymer binder having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, styrene-butadiene copolymer, polyvinyl chloride, polycarbonate, polyamide, melamine resin, phenol resin, epoxy resin, cyclic (alicyclic or aromatic) isocyanate and polyol. And the like obtained by the reaction. Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups and polymers having a halogen atom other than fluorine as a substituent also have a high refractive index. You may use the polymer formed by the polymerization reaction of the monomer which introduce | transduced the double bond and enabled radical hardening.

  In order to obtain a higher refractive index, inorganic fine particles may be dispersed in the polymer binder. The refractive index of the inorganic fine particles is preferably 1.80 to 2.80. The inorganic fine particles are preferably formed from metal oxides or sulfides. Examples of the metal oxide or sulfide include titanium oxide (for example, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, zirconium oxide, and zinc sulfide. Among these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The inorganic fine particles are mainly composed of oxides or sulfides of these metals, and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. An inorganic material that is film-forming and can be dispersed in a solvent, or is itself a liquid, such as alkoxides of various elements, salts of organic acids, coordination compounds bonded to coordination compounds (eg chelate compounds), active inorganics A medium / high refractive index layer can also be formed using a polymer.

  An antiglare function (function of preventing incident scenery from being transferred to the film surface by scattering incident light on the surface) can be imparted to the surface of the antireflection layer. For example, it has an anti-glare function by forming fine irregularities on the surface of the transparent film and forming an antireflection layer on the surface, or by forming irregularities on the surface with an embossing roll after forming the antireflection layer. An antireflection layer can be obtained. An antireflection layer having an antiglare function generally has a haze of 3 to 30%.

  The said hard-coat layer which can be provided in the optical filter of this invention has hardness higher than the hardness of the said transparent support body. The hard coat layer preferably contains a crosslinked polymer. The hard coat layer can be formed using an acrylic, urethane, or epoxy polymer, oligomer, or monomer (for example, an ultraviolet curable resin). A hard coat layer can also be formed from a silica-based material.

  A lubricating layer may be formed on the surface of the antireflection layer (low refractive index layer). The lubricating layer has a function of imparting slipperiness to the surface of the low refractive index layer and improving scratch resistance. The lubricating layer can be formed using polyorganosiloxane (for example, silicon oil), natural wax, petroleum wax, higher fatty acid metal salt, fluorine-based lubricant or derivative thereof. The thickness of the lubricating layer is preferably 2 to 20 nm.

  When the cyanine compound according to the present invention is contained in an optical filter, the above-mentioned “(3) Method for containing in an adhesive layer between any two adjacent members selected from a transparent support and any layer” is adopted. For example, after the cyanine compound or the like according to the present invention is contained in the pressure-sensitive adhesive, the above-described transparent support and any two adjacent layers may be bonded using the pressure-sensitive adhesive. As the pressure-sensitive adhesive, known transparent adhesives for laminated glass such as silicone-based, urethane-based, acrylic-based pressure-sensitive adhesives, polyvinyl butyral adhesives, ethylene-vinyl acetate-based adhesives, and the like can be used. Moreover, when using this adhesive, as needed, crosslinking agents, such as a metal chelate type, an isocyanate type, and an epoxy type, can be used as a hardening | curing agent. Moreover, it is preferable that the thickness of an adhesive layer shall be 2-400 micrometers.

  When employing the above-mentioned “(4) Method for providing a light absorbing layer containing a light absorber such as a cyanine compound according to the present invention separately from each optional layer”, the cyanine compound according to the present invention is used as it is. A light absorption layer can be formed, or a light absorption layer can be formed by dispersing in a binder. Examples of the binder include natural polymer materials such as gelatin, casein, starch, cellulose derivatives, and alginic acid, or polymethyl methacrylate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, styrene-butadiene copolymer, polystyrene, Synthetic polymer materials such as polycarbonate and polyamide are used.

When the binder is used, an organic solvent can be used at the same time. The organic solvent is not particularly limited, and various known solvents can be used as appropriate. For example, alcohols such as isopropanol Ether ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, butyl diglycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, esters such as ethyl acetate, butyl acetate, methoxyethyl acetate; Acrylic esters such as ethyl acrylate and butyl acrylate; fluorinated alcohols such as 2,2,3,3-tetrafluoropropanol; hydrocarbons such as hexane, benzene, toluene and xylene; methylene dichloride, dichloroe Emissions, chlorinated hydrocarbons such as chloroform and the like. These organic solvents can be used alone or in combination.
In the production of the optical filter of the present invention, the concentration of the coating liquid containing the cyanine compound, the organic solvent and other various additives according to the present invention is 1 to 5% by mass, particularly 2 to 3% by mass. preferable.

  The undercoat layer, antireflection layer, hard coat layer, lubricating layer, filter layer, and the like can be formed by a general coating method. As a coating method, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, an extrusion coating method using a hopper (described in US Pat. No. 2,681,294), etc. Is mentioned. Two or more layers may be formed by simultaneous application. For the simultaneous application method, US Pat. No. 2,761,791, US Pat. No. 2,941,898, US Pat. No. 3,508,947, US Pat. No. 3,526,528 and Yuji Harasaki “Coating Engineering”, page 253 (published by Asakura Shoten in 1973) There is a description.

Hereinafter, the present invention will be described in more detail with evaluation examples and examples. However, the present invention is not limited by the following examples.
Evaluation Example 1 shows the solubility evaluation of the cyanine compound and the comparative compound according to the present invention, and Evaluation Example 2 shows the liquid stability evaluation of the cyanine compound and the comparative compound.
Moreover, Examples 1-10 show the preparation examples of the optical filter containing the cyanine compound which concerns on this invention.

[Evaluation Example 1] Solubility Evaluation Compound No. 1 1, no. 2, no. 5, no. 10 and no. 18 and comparative compound No. 1 shown below. 1-No. For No. 5, solubility in ethyl methyl ketone at 20 ° C. was evaluated. The evaluation was performed by adding the cyanine compound to ethyl methyl ketone in 0.25 mass% increments in the range of 0.25 mass% to 5.0 mass%, and observing dissolution and insolubility. The results are shown in [Table 1].

[Evaluation Example 2] Liquid Stability Evaluation A test solution was prepared with the following composition, and left at room temperature for 2 weeks to observe the presence or absence of solid precipitation. The liquid stability was evaluated with ◯ indicating that no solid precipitation was observed, and x indicating that solid precipitation was observed. The results are shown in [Table 2].

(Combination)
Cyanine compound (described in Table 2) 2mg
Diimonium compound (described in [Chemical Formula 9]) 0.1 g
Methyl ethyl ketone 1.0g

[Example 1] Preparation of optical filter 1
A coating liquid was prepared with the following composition, and the coating liquid was applied to a 188 μm-thick polyethylene terephthalate film subjected to easy adhesion treatment by a bar coater # 9 and then dried at 100 ° C. for 3 minutes. An optical filter (cyanine compound content 2.0 mg / m ² ) having a film layer with a thickness of 10 μm was obtained. With respect to this optical filter, when the absorption spectrum was measured with an ultraviolet-visible near-infrared spectrophotometer V-570 manufactured by JASCO Corporation, λmax was 585 nm and the half-value width was 36 nm.

(Combination)
Sumipex LG 2.5g
(Acrylic resin binder manufactured by Sumitomo Chemical Co., Ltd., resin content 40% by mass)
Compound No. 1 2mg
Methyl ethyl ketone 2.5g

[Example 2] Preparation of optical filter 2
Compound No. In place of Compound No. 1 An optical filter (cyanine compound content of 2.0 mg / m ² ) was prepared in the same manner as in Example 1 except that No. 2 was used, and the obtained optical filter was subjected to UV-visible near-infrared by JASCO Corporation. When the absorption spectrum was measured with a spectrophotometer V-570, λmax was 587 nm and the half-value width was 37 nm.

[Example 3] Preparation of optical filter 3
Compound No. In place of Compound No. 1 An optical filter (cyanine compound content of 2.0 mg / m ² ) was prepared in the same manner as in Example 1 except that No. 10 was used. The obtained optical filter was subjected to UV-visible near-infrared made by JASCO Corporation. When the absorption spectrum was measured with a spectrophotometer V-570, λmax was 552 nm and the half-value width was 29 nm.

[Example 4] Preparation of optical filter 4
Compound No. In place of Compound No. 1 An optical filter (cyanine compound content of 2.0 mg / m ² ) was prepared in the same manner as in Example 1 except that No. 18 was used, and the obtained optical filter was subjected to UV-visible near-infrared by JASCO Corporation. When the absorption spectrum was measured with a spectrophotometer V-570, λmax was 482 nm and the half-value width was 49 nm.

[Example 5] Preparation of optical filter 5
Compound No. In place of Compound No. 1 An optical filter (cyanine compound content of 2.0 mg / m ² ) was prepared in the same manner as in Example 1 except that No. 5 was used. The obtained optical filter was subjected to UV-visible near-infrared made by JASCO Corporation. When the absorption spectrum was measured with a spectrophotometer V-570, λmax was 548 nm and the half-value width was 38 nm.

[Example 6] Preparation of optical filter 6
In Example 1 above, the compound No. In addition to 1, an optical filter (cyanine compound content of 2.0 mg / m ² , diimonium compound) was used in the same manner as in Example 1 except that 0.1 g of the diimonium compound represented by the above [Chemical Formula 9] was used. content 100 mg / m ²⁾ create and the obtained optical filter was measured for absorption spectrum in the ultraviolet-visible-near-infrared spectrophotometer V-570 manufactured by JASCO (Ltd.), .lambda.max is 585 nm, half-value width Was 36 nm.

[Example 7] Production of optical filter 7
A pressure-sensitive adhesive solution was prepared by the following composition, and the pressure-sensitive adhesive solution was applied to a 188 μm-thick polyethylene terephthalate film subjected to easy adhesion treatment with a bar coater # 30 and then dried at 100 ° C. for 10 minutes. An optical filter (cyanine compound content 2.0 mg / m ² ) having an adhesive layer having a thickness of about 10 μm on the film was obtained. The optical filter was measured with an ultraviolet-visible near-infrared spectrophotometer V-570 manufactured by JASCO Corporation. As a result, λmax was 585 nm and the half width was 37 nm.

(Combination)
Compound No. 1 2.0mg
Acrylic adhesive (DB Bond 5541: Diabond) 20g
80g of methyl ethyl ketone

[Example 8] Preparation of optical filter 8
In Example 7 above, the compound No. In addition to 1, an optical filter (cyanine compound content of 2.0 mg / m ² , diimonium compound) was used in the same manner as in Example 7 except that 0.1 g of the diimonium compound represented by the above [Chemical Formula 9] was used. content 100 mg / m ²⁾ create and the obtained optical filter was measured for absorption spectrum in the ultraviolet-visible-near-infrared spectrophotometer V-570 manufactured by JASCO (Ltd.), .lambda.max is 585 nm, half-value width Was 36 nm.

[Example 9] Preparation of optical filter 9
The following formulation was melt kneaded with a plastmill at 260 ° C. for 5 minutes. After kneading, a dye-containing pellet was obtained from a nozzle having a diameter of 6 mm using an extrusion water cooling pelletizer. This pellet was formed into a thin plate (cyanine compound content of 2.0 mg / m ² ) having a thickness of 0.25 mm at 250 ° C. using an electric press. When the absorption spectrum of this thin plate was measured with an ultraviolet-visible near-infrared spectrophotometer V-570 manufactured by JASCO Corporation, λmax was 585 m and the half-value width was 36 nm.

(Combination)
Iupilon S-3000 100g
(Mitsubishi Gas Chemical Co., Ltd .; polycarbonate resin)
Compound No. 1 0.01g

[Example 10] Preparation of optical filter 10
A UV varnish was prepared by the following composition, and the UV varnish was applied to a 188 μm-thick polyethylene terephthalate film subjected to an easy adhesion treatment by a bar coater # 9, followed by drying at 80 ° C. for 30 seconds. Thereafter, an optical filter (cyanine compound content of 2.0 mg / m ² ) having a filter layer with a cured film thickness of about 5 μm was obtained by irradiating 100 mJ of ultraviolet rays with a high-pressure mercury lamp with an infrared cut film filter. With respect to this optical filter, when the absorption spectrum was measured with an ultraviolet-visible near-infrared spectrophotometer V-570 manufactured by JASCO Corporation, λmax was 585 nm and the half-value width was 36 nm.

(Combination)
Adekaoptomer KRX-571-65 100g
(Asahi Denka Kogyo's UV curable resin, resin content 80% by mass)
Compound No. 1 0.5g
Methyl ethyl ketone 60g

  From the results of Evaluation Example 1 shown in Table 1, it can be seen that the cyanine compound according to the present invention is excellent in solubility. Further, from the results of Evaluation Example 2 shown in Table 2, the solution containing the cyanine compound according to the present invention and the diimonium compound according to the present invention is excellent in liquid stability, but the comparative compound and the diimonium compound according to the present invention In the solution containing, solid precipitation was observed, and the liquid stability was poor. This is presumably because the anion of the comparative compound and the diimmonium compound was exchanged, and a poorly soluble diimmonium perchlorate was deposited. Further, as apparent from Examples 1 to 10, the optical filter containing the cyanine compound according to the present invention has steep light absorption in the wavelength region of 450 to 620 nm, and is an optical filter for an image display device. It is suitable as.

Claims (9)

An optical filter comprising at least one cyanine compound represented by the following general formula (I):

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. R ¹ and R ² , and R ³ and R ⁴ may be linked to each other to form a ring, and Y ¹ and Y ² each independently represent 1 to 1 carbon atoms. 8 represents an alkyl group, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, and R ⁵ and R ⁶ each independently represents a perhaloalkyl group having 1 to 8 carbon atoms. R ¹ , R ² , R ³ , R ⁴ , Y ¹ and Y ² represented by the above alkyl group having 1 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms and 7 to 20 carbon atoms The arylalkyl group may have a substituent, and the above alkyl group having 1 to 8 carbon atoms. (The methylene group in it may be replaced by —O— or —CH═CH—.) An optical filter comprising at least one cyanine compound represented by the following general formula (II):

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Y ¹ and Y ² are the same as those in the general formula (I), and X ¹ and X ² are each independently , CF ₃ — or CF ₃ O—. An optical filter comprising at least one cyanine compound represented by the following general formula (III):

Wherein R ¹ , R ² , R ⁵ , R ⁶ , Y ¹ and Y ² are the same as those in the general formula (I), and A is a benzene ring or naphthalene which may have a substituent. Represents a ring.) The optical filter according to claim 1, wherein the cyanine compound is contained in an amount of 1 to 1000 mg / m ² per unit area. The optical filter in any one of Claims 1-4 containing the diimonium compound represented by the following general formula (IV).

(Wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an amino group, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ^11. R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , an alkyl group having 1 to 8 carbon atoms, represented by R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ The amino group may have a substituent, and the methylene group in the alkyl group having 1 to 8 carbon atoms may be substituted with —O— or —CH═CH—, and r is 1 It represents the number of to 4, R ⁵ and R ⁶ are as defined for general formula (I).)   The optical filter according to any one of claims 1 to 3 has a multilayer structure including an adhesive layer, and the cyanine compound is contained in the adhesive layer. Optical filter.   6. The optical filter according to claim 5, wherein the cyanine compound and the diimonium compound are contained in the pressure-sensitive adhesive layer.   The optical filter according to claim 1, which is used for an image display device. The optical filter according to claim 8, wherein the image display device is a plasma display.