JP2003036033A - Filter for display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent color adjustment filter or the like which has a sharp absorption at the wavelength range of 480 to 520 nm and 550 to 610 nm, and also has an absorption at the wavelength range of 380 to 420 nm. SOLUTION: This filter for display characteristically contains tetrazaporphyrin pigment indicated by general formula (I) shown below, dipyrazolyl methine pigment indicated by general formula (II) shown below, and dipyrazolyl squarylium pigment indicated by general formula (III) shown below.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display filter having a layer containing a tetraazaporphyrin dye, a dipyrazolylmethine dye and a dipyrazolyl squarylium dye.

[0002]

2. Description of the Related Art Conventionally, as a color image display device, a cathode ray tube, a fluorescent display tube, a field emission, a plasma panel,
Various display devices based on liquid crystal and electroluminescence have been developed. These are in the form of displaying images using a combination of red, blue, and green three-primary color light emission, but at that time, light emission other than the above three primary colors is absorbed by using a so-called band-pass filter to obtain a clear color. It is necessary to obtain an image and correct the color balance of the image. As the band-pass filter, various studies have been conducted using a dye, but in this case, there is no absorption other than the intended absorption, and heat resistance and light resistance of the dye are important factors.

Regarding color adjustment filters for displays, various studies have been made on those which selectively absorb light of a specific wavelength by using commercially available dyes, but in these color adjustment methods, up to the three necessary primary color components are obtained. There is a problem that the color balance becomes poor due to partial absorption and the display screen becomes dark. Further, recently, in JP-A-2000-43175 and the like, although there is a disclosure about an antireflection film containing a squarylium compound, as a specific example of the squarylium compound, there is no disclosure about dipyrazolyl squarylium, and There is no description about the correlation between the structure and the light transmittance at each wavelength.

On the other hand, regarding dipyrazolyl squarylium compounds, Angew. Chem. Internat. Edit., Vol. 7 (1
968), p. 530, discloses that N-phenyl type dipyrazolyl squarylium is an orange dye, but does not describe its absorption spectrum waveform or the like.
Further, US Pat. No. 4,175,956 only discloses N-phenyl type dipyrazolyl squarylium as a red dye useful as an electrophotographic photoreceptor, and does not describe the light transmittance at each wavelength.

In addition, particularly in a plasma display panel, a mixed gas of xenon and neon is excited by discharge and emits vacuum ultraviolet rays, and the red rays due to the vacuum ultraviolet rays,
Since the method of obtaining the three primary color light emission by using the light emission of each of the blue and green phosphors is adopted, 590 nm emitted when the neon atom returns to the ground state after being excited.
There is so-called neon orange light emission centered around
The orange color mixes with the red color, making it difficult to obtain a bright red color. Especially for this orange shielding, the red emission part of the three primary color emission is 600 to 6
Since they are adjacent to each other in the vicinity of 50 nm, it is required that only the orange light is shielded and the red light emission is not affected.

As one of the dyes for absorbing the neon orange light, for example, Japanese Patent Laid-Open No. 2000-275402 is known.
Japanese Patent Publication No. WO 01/10971 discloses an example of a display filter using a tetraazaporphyrin dye, but there is no description about a combination with a dipyrazolyl squarylium compound. Further, in correcting the color balance, usually, a plurality of dyes are used, but in this case, due to the interaction of a plurality of mixed dyes, heat resistance, light resistance, etc. are compared with each dye when used alone. It often goes down.

[0007]

The present invention does not affect the emission of the three primary colors of red, blue and green, and has a sharp absorption in the wavelength range of 480 to 520 nm and the wavelength range of 550 to 610 nm in the light transmittance curve. And 380-420n
An object of the present invention is to provide an excellent color adjustment filter having absorption in the wavelength range of m, a color purity improving filter, a color reproduction range expanding filter, and the like.

[0008]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have proposed a dipyrazolyl squarylium dye represented by the general formula (III) and a tetraazaporphyrin represented by the general formula (I). It was found that the above-mentioned problems can be solved by combining a dye group and a dipyrazolylmethine dye group represented by the general formula (II),
The present invention has been solved. That is, the gist of the present invention is
It contains a tetraazaporphyrin dye represented by the following general formula (I), a dipyrazolylmethine dye represented by the following general formula (II) and a dipyrazolyl squarylium dye represented by the following general formula (III). A display filter characterized in that

[0009]

[Chemical 4]

[In the formula (I), R ^{1 to} R ⁸ are each independently
Hydrogen atom, halogen atom, nitro group, cyano group, hydroxy group, amino group, optionally substituted alkyl group, optionally substituted alkoxy group, optionally substituted group Good aryl group, optionally substituted aryloxy group, optionally substituted alkylamino group, optionally substituted dialkylamino group, optionally substituted Represents an optionally substituted alkylthio group or an arylthio group which may have a substituent, and R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ are linked to each other. An aliphatic carbocycle may be formed. M is two hydrogen atoms, divalent metal atom, trivalent monosubstituted metal atom, tetravalent divalent
A substituted metal atom or an oxymetal atom is shown. ]

[0011]

[Chemical 5]

[In the formula (II), R ⁹ represents an alkyl group which may have a substituent, an aryl group which may have a substituent or a hydrogen atom, and R ¹⁰ represents a substituent. Alkyl group which may have, alkoxy group which may have a substituent, alkoxycarbonyl group which may have a substituent, aryl group which may have a substituent, aryloxy group, It represents an aryloxycarbonyl group which may have a substituent, an amino group which may have a substituent or a hydrogen atom, and R ¹¹ represents an alkyl group which may have a substituent and a substituent. Represents an aryl group or a hydrogen atom which may be present, X represents an oxygen atom or an NH group, and R ¹⁰ , R ¹¹ and X thereof may be different from each other between both pyrazole rings. . ]

[0013]

[Chemical 6]

[In the formula (III), R ¹² represents an alkyl group which may have a substituent, an aryl group which may have a substituent or a hydrogen atom, and R ¹³ represents a substituent. Alkyl group which may have, alkoxy group which may have a substituent, alkoxycarbonyl group which may have a substituent, aryl group which may have a substituent, aryloxy group, An aryloxycarbonyl group which may have a substituent, an amino group which may have a substituent or a hydrogen atom, Y represents an oxygen atom or an NH group, and these R ¹² , R ¹³ , And Y may be different from each other between both pyrazole rings. ].

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In R ^{1 to} R ⁸ of the tetraazaporphyrin dye represented by the general formula (I) used in the filter for display of the present invention, the halogen atom is, for example, a fluorine atom, Examples of the chlorine atom, bromine atom and the like, the alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group, dodecyl group, 1 to 20 carbon atoms such as tridecyl group, pentadecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. , A decyloxy group, an undecyloxy group, a dodecyloxy group, a tridecyloxy group, a pentadecyloxy group and the like having a straight or branched chain having 1 to 20 carbon atoms. Examples of the aryl group include: Examples thereof include a phenyl group and a naphthyl group, and examples of the aryloxy group include a phenoxy group and a naphthyloxy group.
As the alkylamino group or dialkylamino group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group,
Examples thereof include an amino group mono- or di-substituted with a linear or branched alkyl group having 1 to 20 carbon atoms such as an undecyl group, a dodecyl group, a tridecyl group, and a pentadecyl group. Examples of the alkylthio group include a methylthio group. , Ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, decylthio group, undecylthio group, dodecylthio group, tridecylthio group, pentadecylthio group, etc. Examples include branched chains,
Examples of the arylthio group include a phenylthio group and a naphthylthio group.

The substituents of the alkyl group, alkoxy group, aryl group, aryloxy group, alkylamino group, dialkylamino group, alkylthio group and arylthio group include, for example, methyl group, ethyl group, propyl group, Alkyl groups having 1 to 10 carbon atoms such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group; methoxy group, ethoxy group , A propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and the like, an alkoxy group having 1 to 10 carbon atoms; a hydroxyl group; or a fluorine atom, a chlorine atom, a bromine atom or the like. A halogen atom etc. are mentioned.

R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R
⁷ and R ⁸ are linked to each other to form-(CH ₂ ) ₃ -,-(CH ₂ ) ₄ -,-(CH
₂ ) An aliphatic carbocycle such as _5- may be formed. In the general formula (I), R ^{1 to} R ^{8 are} as follows.
(1) optionally having an alkoxy group or a halogen atom as a substituent, a linear or branched alkyl group,
(2) A cycloalkyl group which may have a linear or branched alkyl group as a substituent, (3) an aryl group which may have an alkyl group, an alkoxy group or a halogen atom as a substituent. , (4) a halogen atom, or (5) is preferably linked to form an aliphatic carbocycle, and is preferably a linear or branched alkyl group having 1 to 8 carbon atoms or linked- ( Particularly preferred is the case where CH ₂ ) ₃ — or — (CH ₂ ) ₄ — is formed.

As M in the above general formula (I), preferably two hydrogen atoms; or, inorganic chemical nomenclature 1990
2 genus, 3 genus, 4 genus, 8 genus, 9 of the periodic table based on the year rule
Genus, 10 genera, 11 genera, 12 genera, 13 genera, 14 genera or 15
Divalent metal atom selected from elements belonging to the genus Trivalent 1
A substituted metal atom, a tetravalent disubstituted metal atom or an oxymetal atom is shown, and specific examples thereof include Cu, Zn, Fe, Co, Ni, Ru, Rd, Pd, and the like.
Mn, Sn, Mg, Ti, etc. are mentioned, and as the trivalent mono-substituted metal atom, Al-Cl, Ga-Cl, In-Cl, F
Examples thereof include halogen atoms such as e-Cl and Ru-Cl, and metal atoms mono-substituted with a hydroxyl group or an alkoxy group. Examples of tetravalent di-substituted metals include SiCl ₂ , GeCl ₂ , TiCl ₂ ,
SnCl ₂ , Si (OH) ₂ , Ge (OH) ₂ , Mn (O
H) ₂ , Sn (OH) _{2 and} other halogen atoms, and metal atoms disubstituted with a hydroxyl group or an alkoxy group may be mentioned. Examples of the oxy metal include VO, MnO and TiO.
Of these, VO, Cu, Ni and Co are preferable, and VO and Cu are more preferable.

Preferred specific examples of the tetraazaporphyrin dye of the general formula (I) of the present invention described above are shown below.

[0020]

[Chemical 7]

In the tetraazaporphyrin dye of the present invention, for example, a compound in which the substituent M in the general formula (I) is a Mg atom is reacted with acetic acid to remove the Mg metal atom, so that the M A method for obtaining a compound having two hydrogen atoms, and the substituent M in the general formula (I) is Mg.
A compound in which M is a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom as defined above is obtained by reacting various metal salts with a compound that is an atom. J.Gen.Chem.USSR, vol.47,1954-1
It can be synthesized according to the method described in 958 (1977) or by combining other known methods.

Examples of the alkyl group in R ⁹ and R ¹¹ of the dipyrazolylmethine dye represented by the general formula (II) used in the display filter of the present invention include a methyl group, an ethyl group and a propyl group. , Butyl, pentyl, hexyl, heptyl, octyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Examples thereof include linear, branched or cyclic ones having a number of 1 to 20, and examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the substituent of the alkyl group and the aryl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
C1-C10 alkyl group such as octyl group, decyl group; carbon number such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group 1-10 alkoxy groups; aryl groups such as phenyl groups and naphthyl groups; aryloxy groups such as phenoxy groups and naphthyloxy groups; sulfonamide groups; alkylsulfonamide groups; dialkylsulfonamide groups; nitro groups; hydroxyl groups; Examples thereof include halogen atoms such as fluorine atom, chlorine atom and bromine atom.

R ⁹ and R ¹¹ are (1) an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, or a linear or branched alkyl group which may have a halogen atom as a substituent. , (2) alkyl group, alkoxy group, sulfonamide group, alkylsulfonamide group, dialkylsulfonamide group, nitro group, hydroxyl group,
Alternatively, an aryl group optionally having a halogen atom as a substituent, and (3) a hydrogen atom are preferable, and R ⁹ is particularly preferably a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. , Or a phenyl group is preferred, and R ¹¹ is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, or a phenyl group which may have an alkyl group or a halogen atom as a substituent. .

Examples of the alkyl group in R ¹⁰ of the general formula (II) include the same alkyl groups as described in the above R ⁹ and R ¹¹ , and the alkoxy group includes
For example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, pentadecyloxy group. Examples thereof include linear or branched ones having 1 to 20 carbon atoms such as a group, examples of the alkoxycarbonyl group include a carbonyl group having the above alkoxy group, and examples of the aryl group include the above R ⁹ and R ¹¹
The same aryl group as described in the above section is mentioned, the aryloxy group includes a phenoxy group, a naphthyloxy group and the like, and the aryloxycarbonyl group includes a carbonyl group having the above aryloxy group.

The alkyl group, alkoxy group, alkoxycarbonyl group, aryl group, aryloxy group,
Examples of the substituent of the aryloxycarbonyl group and the amino group include, for example, the same alkyl group, the same alkoxy group, the same aryl group and the same aryloxy as those mentioned as the substituents of the alkyl group and the aryl group in R ⁹ and R ¹¹ . Group, similarly sulfonamide group, similarly alkylsulfonamide group, similarly dialkylsulfonamide group, similarly nitro group, similarly hydroxyl group, similarly halogen atom, as well as an acyl group such as propionyl group, butyryl group, benzoyl group; or a methanesulfonyl group, Examples thereof also include a sulfonyl group such as a benzenesulfonyl group.

R ¹⁰ is (1) an alkoxy group,
Aryl group, aryloxy group, hydroxyl group, or may have a halogen atom as a substituent, a linear or branched alkyl group, (2) may have an alkoxy group as a substituent, A chain or branched alkoxy group, (3) an alkoxycarbonyl group optionally having an alkoxy group as a substituent, (4) an alkyl group, an alkoxy group, a sulfonamide group, an alkylsulfonamide group, a dialkylsulfonamide Group, nitro group, hydroxyl group,
Alternatively, it may have a halogen atom as a substituent,
Aryl group, (5) alkyl group, or a carbonyl group having an aryloxy group which may have an alkoxy group as a substituent, or (6) an alkyl group, an acyl group, or a sulfonyl group as a substituent Optionally, an amino group is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms is particularly preferable.

In the general formula (II), X is preferably an oxygen atom. Further, in the present invention, as the dipyrazolylmethine dye represented by the general formula (II),
R ¹⁰ , R ¹¹ and X may be different from each other between both pyrazole rings, but are preferably symmetrical with a methine group sandwiched therebetween. Preferred specific examples of dipyrazolylmethine dyes are shown below. Shown in.

[0029]

[Chemical 8]

The dipyrazolylmethine dye is, for example, a pyrazolone compound 2 corresponding to the general formula (II).
1 mole of ortho-formic acid alkyl ester compound per mole
Mol to heat and reflux without solvent for condensation reaction.
igs Ann. Chem., 1680 to 1688 (1976), or according to the above reaction, N-methylpyrrolidone, N, N
-Dimethylformamide, dimethylsulfoxide, 1,
In a solvent such as 3-dimethyl-2-imidazolidinone, 90
It can be synthesized by heating to about 200 ° C. or by combining other known methods.

The alkyl group and aryl group in R ¹² of the dipyrazolyl squarylium dye represented by the general formula (III) used in the filter for display of the present invention include R ⁹ and R ^{9 in the} general formula (II). The same alkyl group and aryl group as those mentioned in the R ¹¹ part can be mentioned. Further, also as the substituent of the alkyl group and the aryl group, in the portion of R ⁹ and R ^{11 in} the general formula (II), the same alkyl group, alkoxy group, and the like as the substituents of the alkyl group and the aryl group, Examples thereof include an aryl group, an aryloxy group, a sulfonamide group, an alkylsulfonamide group, a dialkylsulfonamide group, a nitro group, a hydroxyl group, and a halogen atom.

R ¹² is (1) an alkoxy group,
An aryl group, an aryloxy group, a hydroxyl group, or a linear or branched alkyl group which may have a halogen atom as a substituent, or (2) a linear or branched alkyl group or an alkoxy group , A sulfonamide group, an alkylsulfonamide group, a dialkylsulfonamide group, a nitro group, a hydroxyl group, or an aryl group which may have a halogen atom as a substituent, is particularly preferable.
1 carbon atom which may have an alkoxy group as a substituent
-8 straight-chain or branched-chain alkyl groups are preferable.

As the alkyl group, alkoxy group, alkoxycarbonyl group, aryl group, aryloxy group, and aryloxycarbonyl group for R ¹³ ,
An alkyl group, an alkoxy group, an alkoxycarbonyl group, which are the same as those mentioned in the R ¹⁰ part of the general formula (II),
Examples thereof include an aryl group, an aryloxy group, and an aryloxycarbonyl group.

Further, the above-mentioned alkyl group, alkoxy group, alkoxycarbonyl group, aryl group, aryloxy group,
As the aryloxycarbonyl group and the substituent of the amino group, in R ¹⁰ of the general formula (II), an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an aryloxy group, an aryloxycarbonyl group,
And the same as the substituents of the amino group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfonamide group, an alkylsulfonamide group, a dialkylsulfonamide group, a nitro group, an acyl group, a sulfonyl group, a hydroxyl group, And a halogen atom and the like.

R ¹³ is (1) an alkoxy group,
Aryl group, aryloxy group, hydroxyl group, or may have a halogen atom as a substituent, a linear or branched alkyl group, (2) may have an alkoxy group as a substituent, A chain or branched alkoxy group, (3) an alkoxycarbonyl group which may have an alkoxy group as a substituent, (4) a linear or branched alkyl group, an alkoxy group, a sulfonamide group, an alkyl sulfone Amide group, dialkylsulfonamide group,
A nitro group, a hydroxyl group, or an aryl group optionally having a halogen atom as a substituent, (5) an alkyl group, or a carbonyl group having an aryloxy group optionally having an alkoxy group as a substituent, or ( 6) A linear or branched alkyl group, an acyl group, or an amino group which may have a sulfonyl group as a substituent is preferable, and particularly, a carbon number which may have an alkoxy group as a substituent. A linear or branched alkyl group having 1 to 8 is preferable.

In the general formula (III), Y is preferably an oxygen atom. Further, in the dipyrazolyl squarylium dye represented by the general formula (III), R ¹² , R ¹³ and Y may be different from each other in both pyrazole rings, but a squarylium group is sandwiched therebetween. And those which are bilaterally symmetrical are preferable, and specific examples of preferable dipyrazolyl squarylium dyes are shown below.

[0037]

[Chemical 9]

The dipyrazolyl squarylium dye can be prepared by, for example, condensing 1 mol of squaric acid with 2 mol of the pyrazolone compound corresponding to the general formula (III), Angew. Chem., Vol. 77,680 to 681 (1965), or by combining other known methods. The wavelength showing the minimum value of the transmittance in the light transmittance curve of the tetraazaporphyrin dye represented by the general formula (I) is 550 to 61.
0 nm, preferably 580-600 nm,
The dipyrazolylmethine dye represented by (II) is 380 to 4
20 nm, and the dipyrazolyl squarylium dye represented by the general formula (III) has a wavelength of 480 to 520 nm.

The display filter of the present invention is characterized by containing the above-mentioned three kinds of compounds. Further, the half width at each minimum value of the light transmittance curve of the filter is preferably 60 nm or less. Particularly, the absorption curve of the tetraazaporphyrin dye and the absorption curve of the portion corresponding to the dipyrazolyl squarylium dye preferably have a sharp valley type, and the minimum value of the transmittance at that wavelength is the tetraazaporphyrin dye. Is preferably 35% or less, and more preferably 30% or less. For dipyrazolylsqualiliu type dyes,
It is preferably 5% or less, more preferably 50% or less.

450 nm, 550 located between the minimum values
The transmittance at 60 nm and 650 nm is preferably 60% or more, more preferably 70% or more. As a result, blue emission around 430 to 470 nm, which is the emission color of the phosphor,
Green emission centered around 530 nm and 600 to 6
It does not block the red emission around 40 nm, can efficiently shield the neon emission around 590 nm, and can adjust the color tone, improve the color purity, and improve the color temperature.

The display filter of the present invention contains the tetraazaporphyrin type dye, the dipyrazolylmethine type dye and the dipyrazolyl squarylium type dye, and the typical form of the inclusion thereof is the tetraazaporphyrin type dye. For porphyrin dyes, dipyrazolylmethine dyes and dipyrazolyl squarylium dyes, a laminate of dye-containing resins consisting of respective binder resins containing each dye, the tetraazaporphyrin dye, dipyrazolylmethine dye and dipyrazolyl squarylium Examples thereof include a single layer sheet or film of a dye-containing resin made of a binder resin containing a mixture of a series of dyes, or a laminate in which these are laminated on a sheet-shaped or film-shaped transparent substrate.

The display filter of the present invention has excellent heat resistance and light resistance even if the tetraazaporphyrin dye, the dipyrazolylmethine dye and the dipyrazolyl squarylium dye are contained in the same layer. . Therefore, it is preferable that the three kinds of dyes are contained in the same layer from the viewpoint of the convenience of the manufacturing process, but they may be contained in different layers to be laminated. In that case, delicate color adjustment can be performed by changing the binder resin of each layer according to the dye used.

Then, in order to produce a laminated body, for example,
1) A method in which a dye and a binder resin are made into a solution or dispersion of an appropriate solvent and applied on a sheet-shaped or film-shaped transparent substrate by a known coating method and dried, and 2) a conventional method for thermoplastic resins. According to the molding method, the dye and the binder resin are melt-kneaded and extruded, injection molded, molded into a film or sheet by compression molding or the like, and the film or sheet is adhered to the transparent substrate with an adhesive or the like, 3) A method in which the dye and the binder resin are melt-kneaded and extruded in a film or sheet form, and extrusion-laminated on a transparent substrate. 4) The dye and the binder resin are melt-kneaded and used together with a transparent resin substrate. Various methods such as an extrusion method can be adopted, and for producing a single-layer sheet or film, for example, 1) the above-mentioned dye and binder Cast onto a carrier and a fat as a solution or dispersion of a suitable solvent, method of drying,
2) A method of forming a film or sheet by melt-kneading the dye and the binder resin and then forming the film or sheet by extrusion molding, injection molding, compression molding, or the like, according to a conventional molding method for a thermoplastic resin.

Among the above-described forms of inclusion and the method for producing the same,
As the display filter of the present invention, a solution or dispersion of the dye and the binder resin in a suitable solvent is applied onto a sheet-shaped or film-shaped transparent substrate by a known coating method and dried to obtain a transparent film. It is preferably a laminate in which a dye-containing resin layer made of a binder resin containing the dye is formed on a substrate.

In the present invention, the method of producing a filter for a display may be a method according to the layer constitution, layer material and the like in each filter application. In the filter for a plasma display panel, which is particularly preferable in the present invention, The method described in 1. is suitable. The material of the transparent base material that constitutes the filter for the plasma display panel of the present invention is not particularly limited as long as it is a material that is substantially transparent and does not significantly absorb or scatter. Specific examples include glass, polyolefin resin, amorphous polyolefin resin, polyester resin, polycarbonate resin, acrylic resin, polystyrene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyarylate. Examples thereof include resins and polyether sulfone resins, and among these, amorphous polyolefin resin, polyester resin, polycarbonate resin, acrylic resin, polyarylate resin, polyether sulfone resin and the like are particularly preferable.

The above-mentioned resin is molded into a film or sheet by a known method such as injection molding, T-die molding, calender molding, compression molding, or a method of casting by melting in an organic solvent. The resin may be mixed with generally known additives, heat antiaging agents, lubricants, antistatic agents and the like. The thickness is preferably in the range of 10 μm to 5 mm. The base material forming such a transparent substrate may be unstretched or stretched. Further, it may be laminated with another base material.

Further, the transparent substrate is subjected to corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, surface roughening treatment,
Surface treatment by a conventionally known method such as chemical treatment, or coating with an anchor coating agent or a primer may be performed. The binder resin is not particularly limited as long as it is a material that is substantially transparent and has small light absorption and scattering. For example, acrylic resin, ethylene-
Vinyl acetate copolymer resin and saponified product thereof, ethylene-vinyl alcohol copolymer resin, polystyrene resin, polyester resin, polycarbonate resin, polyamide resin, polysulfone resin, polyvinyl acetate resin,
Examples thereof include polyvinyl butyral-based resin, AS resin, PVPA, nylon, cellulose acetate-based resin, cellulose-based resin, phenol-based resin, and phenoxy-based resin, and among these, polyester-based resin and acrylic-based resin are preferable.

Examples of the solvent include alkanes such as butane, pentane, hexane, heptane and octane;
Cycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; alcohols such as ethanol, propanol, butanol, amyl alcohol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, furfuryl alcohol; methyl cellosolve, Cellosolves such as ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether. acetate, Propylene glycols such as propylene glycol dimethyl ether; ketones such as acetone, methyl amyl ketone, cyclohexanone, acetophenone; ethers such as dioxane, tetrahydrofuran; butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate , Ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, etc .; halogenated hydrocarbons such as chloroform, methylene chloride, tetrachloroethane; benzene, toluene, xylene , Aromatic hydrocarbons such as cresol; highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like.

In the solution or dispersion of the dipyrazolyl squarylium compound and the binder resin, polyvinyl butyral resin, phenoxy resin,
A dispersant such as a phenol resin such as a rosin-modified phenol resin, a petroleum resin, a cured rosin, a rosin ester, a rosin resin such as a maleinized rosin, or a polyurethane resin may be used.

The dispersant is usually added in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the dipyrazolyl squarylium dye used. Further, the dye (the total amount of the tetraazaporphyrin dye, the dipyrazolylmethine dye and the dipyrazolyl squarylium dye) and the binder resin, and the concentration of the dispersant used as a solution or dispersion. Is
Usually, it is 0.5 to 50% by weight, and the total amount of the dye (the total amount of the tetraazaporphyrin dye, the dipyrazolylmethine dye and the dipyrazolyl squarylium dye), the binder resin, and the dispersant. The proportion of the above-mentioned dye in the above is usually 0.05 to 50% by weight, preferably 0.1 to 20% by weight.

Further, the tetraazaporphyrin dye,
In the dipyrazolylmethine dye and the dipyrazolyl squarylium dye, when the amount of the tetraazaporphyrin dye is 1, the dipyrazolylmethine dye is
The dipyrazolyl squarylium dye is used at a ratio of about 2-1 and about 0.1 to 1.5. In general, if the amount of the dipyrazolyl squarylium dye is too small, the filter becomes greenish, and if too much, it becomes reddish.

The method for applying the solution or dispersion on the transparent substrate is, for example, a dip coating method, a flow coating method, a spray coating method, a bar coating method, a gravure coating method, a roll coating method or a blade coating method. , Air knife coating method, etc., and the coating amount thereof is usually 0.1 to 30 μm as a dry film thickness, preferably 0.5 to
The range is 10 μm.

As described above, the display filter of the present invention is formed of a resin layer composed of a binder resin containing a mixture of the tetraazaporphyrin dye, the dipyrazolylmethine dye and the dipyrazolyl squarylium dye. A single layer sheet or film, or a laminate formed by laminating layers made of binder resins containing respective dyes, as a dye-containing layer on a sheet-shaped or film-shaped transparent substrate. The display filter of the present invention further comprises, in the dye-containing resin, an anthraquinone type, an azo type, a phthalocyanine type, and a pyrromethene which absorb visible light such as yellow light, red light, and blue light. System, cyanine system, tetraazaporphyrin system other than the above, and other than the above Arylium-based, or may contain a dye such as a methine-based other than the above, as the containing form, the tetraazaporphyrin-based dye, the dipyrazolylmethine-based dye and the dipyrazolyl squarylium-based dye-containing resin May coexist with each other, or a separate layer may be provided.

The display filter of the present invention preferably further contains an antioxidant and an ultraviolet absorber. As a form of containing these, it is preferable that the antioxidant coexists in the dye-containing resin layer, and the ultraviolet absorber may coexist in the resin layer. Is preferably provided as a layer of, for example, the tetraazaporphyrin dye, the dipyrazolylmethine dye, and the dipyrazolyl squarylium dye-containing resin by a coating method using the same binder resin as mentioned above, Normally 0.
With a film thickness of 1 to 30 μm, preferably 0.5 to 10 μm,
Alternatively, it can be formed by including it in the transparent substrate. Incidentally, when the ultraviolet absorber-containing layer is provided as a layer independent of the tetraazaporphyrin dye, the dipyrazolylmethine dye and the dipyrazolyl squarylium dye-containing resin layer, the ultraviolet absorber layer is used as a filter. Sometimes the outer side of the dye-containing resin layer, that is, laminated so as to be present on the side opposite to the display adhesive surface, or to make the ultraviolet absorber coexist with the ultraviolet absorber in the layer located on the external side. preferable.

Examples of the antioxidant include 2,6-di-t-butyl-p-cresol and 2,6.
-Di-t-butyl-4-hydroxymethylphenol,
2,6-di-t-butyl-4-ethylphenol, 2,
4,6-Tris-t-butylphenol, n-octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, stearyl-β-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,
4'-isopropylidene bisphenol, 4,4'-methylene bis (2,6-di-t-butylphenol),
4,4'-butylidene bis (3-methyl-6-t-butylphenol), 1,1-bis (4'-hydroxyphenyl) cyclohexane, 2,6-bis (2'-hydroxy-3'-t-butyl-) 5'-methylbenzyl) -4-
Methylphenol, 2,2'-thiobis (4-methyl-
6-t-butylphenol), 4,4′-thiobis (2
-Methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol),
1,1,3-Tris (2'-methyl-4'-hydroxy-5'-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 ', 5'- The-t-
Butyl-4'-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxyphenyl)
Isocyanurate, tris [β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane and other phenolic compounds, dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate and other sulfur System, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite,
Tris (nonylphenyl) phosphite, tris (mono- and di-nonylphenyl) phosphite, 4,4′-butylidene bis (3-methyl-6-t-butylphenyl)
Examples thereof include phosphorus-based compounds such as ditridecyl phosphite, distearyl pentaerythritol diphosphite, and trilauryl trithiophosphite. Of these, phenol-based antioxidants or phosphorus-based antioxidants are preferable.
The amount of the antioxidant added is usually 1 part of the binder resin.
It is used in an amount of 0.01 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 00 parts by weight. When the above-mentioned antioxidant is used in excess, strong light hits the antioxidant, and the antioxidant itself is oxidized to induce a chain oxidation reaction of the squarylium-based dye, which is rather the light resistance of the squarylium-based dye. In that case, it is preferable to use an ultraviolet absorber together.

Examples of the ultraviolet absorber include, for example,
2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) Benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-
Amylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl)
Benzotriazoles such as -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole,
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Octyloxybenzophenone, 2-hydroxy-4-
Benzophenone compounds such as dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl Salicylates such as salicylate, hexadecyl-2,5-t-butyl-4-hydroxybenzoate, 2,4-di-t-
Butylphenyl-3 ', 5'-di-t-butyl-4'-
Organic UV absorbers such as benzoate such as hydroxybenzoate, titanium oxide, zinc oxide, cerium oxide,
Inorganic ultraviolet absorbers such as iron oxide and barium sulfate can be used. Among these, the wavelength exhibiting 50% transmittance is 350 to 420 nm from the viewpoint of ultraviolet absorption and absorption ability and non-colorability.
Is preferable, and that in the range of 360 to 400 nm is particularly preferable.

Instead of providing the layer containing the ultraviolet absorber, a commercially available ultraviolet cut filter, for example, "Sharp cut filter SC-3 manufactured by Fuji Photo Film Co., Ltd."
8 "," SC-39 "," SC-40 "," Acryprene "manufactured by Mitsubishi Rayon Co., etc. may be laminated. In addition, the display filter of the present invention is an additive such as an antistatic agent, a lubricant, a release agent, a flame retardant, a flame retardant aid, a filler, etc., as long as the effects of the present invention are not impaired. May be contained in an appropriate form.

The display filter of the present invention, particularly the plasma display panel filter, further comprises a near-infrared absorbing layer, an electromagnetic wave shielding layer, a light ray antireflection layer,
A glare-preventing (non-glare) layer, a scratch-preventing layer, and the like may be provided, and the arrangement of each layer in the filter may be arbitrarily selected, but the layers are preferably laminated in this order. The thickness of each of these layers is usually 0.1 to 30 μm, preferably 0.5 to 10 μm.

Here, the near-infrared absorbing layer may be formed as an independent layer by incorporating the near-infrared absorbing agent into the binder resin as described above, but a filter produced by using the near-infrared absorbing agent as a laminate. Used between each layer of,
It can also be formed by adding it to any one of filter constituent layers such as an adhesive layer or a scratch-preventing layer described later, or a layer composed of an anchor coating agent used as appropriate. This near-infrared absorbing layer preferably has a near-infrared transmittance of 10% or less at 800 to 1000 nm.

Examples of the near infrared ray absorbing agent include nitroso compounds and their metal complex salts, cyanine compounds,
Thiol nickel complex salt type compound, dithiol nickel complex salt type compound, aminothiol nickel complex salt type compound, phthalocyanine type compound, naphthalocyanine type compound, triallylmethane type compound, immonium type compound, diimonium type compound, naphthoquinone type compound, anthraquinone type compound, Amino compounds, aminium salt-based compounds, and other organic substances such as squarylium-based compounds and methine-based compounds, antimony-doped tin oxide, indium-doped tin oxide, and other IUPAC inorganic chemistry nomenclature 1990
Examples thereof include inorganic substances such as oxides, carbides, and borides of metals belonging to Groups 4, 5, and 6 of the periodic table based on the year rule.

The electromagnetic wave shielding layer is provided in order to prevent the electromagnetic waves generated by the light emission from the display device from adversely affecting the living body and the electronic equipment. The electromagnetic wave shielding layer is
It consists of thin films of metals or metal oxides such as silver, copper, indium oxide, zinc oxide, indium tin oxide, antimony tin oxide, etc., which are vacuum deposition method, ion plating method, sputtering method, CVD method, plasma chemistry. It can be manufactured by utilizing a conventionally known dry plating method such as a vapor deposition method. The most commonly used electromagnetic wave shielding layer is a thin film of indium tin oxide (sometimes abbreviated as ITO), but a copper thin film having a mesh-shaped hole or a dielectric layer and a metal layer as a base material. A laminated body in which the layers are alternately laminated on top can also be preferably used. The dielectric layer is a transparent metal oxide such as indium oxide and zinc oxide, and the metal layer is generally silver or a silver-palladium alloy. The laminated body is usually laminated so that it starts from the dielectric layer and has an odd number of layers between about 3 and 13 layers.

The electromagnetic wave shielding layer may be formed as it is on any layer of the above-mentioned display filters, or may be formed by vapor deposition or sputtering on a resin film or glass and then pasting the filter. . The antireflection layer is for suppressing reflection on the surface and preventing external light such as a fluorescent lamp from being reflected on the surface. The antireflection layer is made of a thin film of an inorganic material such as a metal oxide, a fluoride, a silicide, a boride, a carbide, a nitride, and a sulfide, and a single layer of a resin having a different refractive index such as an acrylic resin or a fluororesin. Alternatively, it may be composed of multiple layers. In the former case, the same dry plating method as that mentioned for the electromagnetic wave shielding layer is used to form the display filter in the form of a single layer or multiple layers. Examples thereof include a method of forming it on the layer as it is, and a method of forming it on the resin film or glass by vapor deposition or sputtering and then adhering it to the filter. In the latter case, a usual method for producing a resin laminate may be used, such as a method in which a film or sheet of a resin such as an acrylic resin or a fluororesin used is adhered to a display filter with an adhesive. Also,
In addition to this, a method in which a film subjected to antireflection treatment is attached to the filter may be used.

The non-glare layer is made by converting fine powder of silica, melamine resin, acrylic resin or the like into an ink, and coating it on any layer of the filter of the present invention by a conventionally known coating method, and heat or light curing. It is formed by Also, a non-glare-treated film may be stuck on the filter. Further, the scratch-preventing layer is a conventionally known coating method using a coating solution prepared by dissolving or dispersing an acrylate such as urethane acrylate, epoxy acrylate, or a polyfunctional acrylate and a photopolymerization initiator in an organic solvent. It is formed by coating, drying, and photo-curing on that layer, preferably on the outermost layer.

The filter for display of the present invention, particularly the filter for plasma display panel is preferably the transparent substrate, the tetraazaporphyrin dye, the dipyrazolylmethine dye and the dipyrazolyl squarylium dye. The containing resin layer as a basic constituent layer, and if necessary, the antioxidant layer, the ultraviolet absorber containing layer, the near infrared absorbing layer, the electromagnetic wave shielding layer, the light reflection preventing layer, the non-glare layer, and the The laminate has a scratch-preventing layer and the like, but the order of laminating each of these layers is not particularly limited, and the laminating method is also not particularly limited. Usually, while sandwiching a transparent substrate between each layer as needed, it is a laminate using an adhesive, in which case, such as corona discharge treatment, glow discharge treatment, plasma treatment, flame treatment, chemical treatment By applying a surface treatment or using a known anchor coating agent such as isocyanate-based, polyester-based, polyethyleneimine-based, polybutadiene-based, alkyl titanate-based, etc., the adhesion at the time of adhesion is improved and the adhesive is even It is preferable because it can be applied.

The display filter of the present invention may be provided with an adhesive layer as the outermost layer for adhering the filter to the display surface of the display. With this pressure-sensitive adhesive layer, the filter can be easily attached to the front surface of the display, for example, during the manufacturing process of the display or after the manufacturing of the display. By doing so, conventionally, it was necessary to sequentially arrange the near-infrared absorption filter, the electromagnetic wave shielding filter, etc. on the front surface of the display itself, but only by attaching the filter of the present invention, the manufacturing process is simplified. not only,
Since the filter is formed integrally with the display, it is possible to reduce the thickness of the entire display device.

As the adhesive constituting the adhesive layer, rubbers such as styrene-butadiene rubber, polyisoprene rubber, polyisobutylene rubber, natural rubber, neoprene rubber, chloroprene rubber, butyl rubber and polymethyl acrylate,
Examples thereof include low polymerization degree resins such as polyacrylic acid alkyl esters such as ethyl polyacrylate and polybutyl acrylate. These may be used alone, but as tackifiers, piccolite, polyvale, rosin ester, etc. You may use what added.

When the surface of the display itself has a high temperature, gas may be generated by heating. In such a case, it is necessary to add a gas absorbent or the like. For this reason, the preferred adhesive is 3
A 30 μm polyester film is attached to a 30 mm glass plate with a 30 μm adhesive, and a 180 ° peel strength after holding at 80 ° C. for 10 days is 300 g / cm or more, preferably 400 g / cm or more. It is desirable to use.

As the method for forming the pressure-sensitive adhesive layer, specifically,
The above rubbers or low polymerization degree resins are dispersed in a solvent system in which a solvent selected from a halogen system, an alcohol system, a ketone system, an ester system, an ether system, an aliphatic hydrocarbon system or an aromatic hydrocarbon system, or a mixture thereof is used. Dissolved and adjusted viscosity, dipping method, flow coating method, spray method,
Coating is carried out by a known coating method such as bar coating method, gravure coating method, roll coating method, blade coating method and air knife coating method, and then the solvent is dried to form an adhesive layer.

The thickness of the pressure-sensitive adhesive layer at this time is usually 5 to 1
The thickness is 00 μm, preferably 10 to 50 μm. It is also possible to provide a release film on the surface of the pressure-sensitive adhesive layer and protect the pressure-sensitive adhesive layer until it is attached to the surface of the plasma display so that dust and the like do not adhere to the pressure-sensitive adhesive layer. In this case, between the pressure-sensitive adhesive layer at the edge of the filter and the peeling film, a part without a pressure-sensitive adhesive layer is formed, or a non-tacky film is sandwiched to form a non-tacky part, and peeling is started. If it is a part, it will be easier to work when attaching.

When a filter is attached to the plasma display, if air bubbles enter between the surface of the plasma display and the filter, the image will be distorted or difficult to see. You need to be careful. The display filter of the present invention may be directly attached to the display surface as described above, or may be further attached to a transparent glass or a transparent resin plate in advance and then attached to the display surface. good.

[0071]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Example 1 0.0050 g of a tetraazaporphyrin dye of I-1 as the dye represented by the general formula (I), and a dipyrazolylmethine dye of II-3 as the dye represented by the general formula (II) 0.0010 g, as the dye represented by the general formula (III), a dipyrazolyl squarylium dye of III-4 of 0.3.
0.25 g of a dye solution prepared by dissolving 0019 g in 0.795 g of toluene was mixed with 1.0 g of a 20 wt% dimethoxyethane solution of an acrylic resin (“DIANAL BR-80” manufactured by Mitsubishi Rayon Co., Ltd.) as a binder resin. Then, a polyethylene terephthalate film (100 μm in thickness, “PET film T100E” manufactured by Mitsubishi Kagaku Polyester Film Co., Ltd.) as a transparent substrate was applied using a bar coater and dried to form a resin layer containing a diphenyl squarylium compound having a film thickness of 6 μm. By forming, a filter for a plasma display panel was produced.

Regarding the obtained plasma display panel filter, a spectrophotometer ("U-3 manufactured by Hitachi Ltd."
500 ”) was used to measure the light transmittance, and the transmittance curve is shown in FIG. The wavelength at the minimum value of transmittance is 59
2 nm (transmittance 10.91%) and 504 nm (transmittance 40.39%), there is no large minimum value in the region other than both minimum values, and the visible light transmittance is 64.61%, and , L ^* a ^* b specified in JIS Z8729
^* Luminance L ^* and color coordinates a ^* , b ^* in the color system are 2 °
In the field of view and C light source, L ^* = 84.082, a ^* =
9.668, b ^* = -11.913, which has little obstruction to the emission of the three primary colors of red, blue, and green of the plasma display panel, does not reduce the brightness of the visual field, and has excellent neon emission shielding properties. It was confirmed that the filter was toned in blue.

Further, after leaving this filter in a constant temperature bath at 100 ° C. for 100 hours, the absorbance was measured with a spectrophotometer (“U-3500” manufactured by Hitachi Ltd.) to determine the residual rate of the dye and the residual rate. Was calculated to be 400n
m is 98.5%, 503 nm is 99.2%, 592 nm
It was 99.4%, and it was confirmed that the heat resistance was excellent.

The I-1 tetraazaporphyrin color
Create a filter similar to the above, using only primes
And L^*a^*b^*Lightness L in color system^*, Color coordinate a^*,
b^*Is 2 ° field of view, C light source, L^*= 88.65
6, a^*= -1.451, b ^*= -19.236
It was a blue filter. Example 2 Purple was formed on the dye-containing resin layer of the filter obtained in Example 1.
Outside line cut filter (Sharp cut filter SC
-39 (Fuji Photo Film Co., Ltd.) laminated for light resistance
A good plasma display panel filter
Made

In a xenon fade meter (“FAL-25AX-HC.B.EC” manufactured by Suga Test Instruments Co., Ltd.), an illuminance of 73,000 lux and a black panel temperature of 6
Under the conditions of 3 ° C. and 33% relative humidity, the ultraviolet absorption layer was used as the exposed surface for 80 hours of exposure, and then the absorbance was measured with the same spectrophotometer as described above. The rate was calculated to be 100 at 400 nm.
%, 100% at 503 nm, and 99.4% at 592 nm, and it was confirmed that the light resistance was excellent.

Example 3 As the compound represented by the general formula (I), 0.0065 g of a tetraazaporphyrin dye I-2, the general formula (II)
As a compound represented by, the dipyrazolylmethine dye of II-3 0.0013 g, as a compound represented by the general formula (III), dipyrazolyl squarylium dye 0.0024 g of III-4 in 1.034 g of toluene 0.25 g of the dissolved dye solution, and an acrylic resin as a binder resin (“DIANAL BR-8 manufactured by Mitsubishi Rayon Co., Ltd.”
0) 20% by weight dimethoxyethane solution (1.0 g) was mixed, and then applied to a polyethylene terephthalate film (thickness 100 μm, “PET film T100E” manufactured by Mitsubishi Kagaku Polyester Film Co., Ltd.) as a transparent substrate using a bar coater. Then, by drying and forming a resin layer containing a diphenyl squarylium compound having a film thickness of 6 μm, a filter for a plasma display panel was produced.

Regarding the obtained plasma display panel filter, a spectrophotometer ("U-3 manufactured by Hitachi Ltd."
500 ") was used to measure the light transmittance, and the transmittance curve is shown in FIG. The wavelength at the minimum value of transmittance is 58
4 nm (transmittance 16.88%) and 504 nm (transmittance 40.43%), there is no large minimum value in the region other than both minimum values, and the visible light transmittance is 64.84%. , L ^* a ^* b specified in JIS Z8729
^* Luminance L ^* and color coordinates a ^* , b ^* in the color system are 2 °
L ^* = 84.380, a ^* = 1 in the field of view and C light source
6.599, b ^* = -11.356, which has little obstruction to the emission of the three primary colors of red, blue and green of the plasma display panel, has no reduction in the brightness of the field of view, and has a dark purple color with excellent shielding properties for neon emission. It was confirmed that the filter was toned.

Further, this filter was left in a constant temperature bath at 100 ° C. for 100 hours, and then the absorbance was measured using a spectrophotometer (“U-3500” manufactured by Hitachi Ltd.) to determine the residual rate of dye and the residual rate. Was calculated to be 400n
m was 100%, 503 nm was 99.1%, and 583 nm was 100%, and it was confirmed to be excellent in heat resistance.

When a filter was prepared in the same manner as above using only the tetraazaporphyrin dye of I-2, the lightness L ^* in the L ^* a ^* b ^* color system, the color coordinate a ^* ,
b ^* is L ^* = 87.59 in a 2 ° field of view and a C light source.
It was 0, a ^* = 7.320, b ^* =-21.063, and it was a purple filter. Example 4 On the dye-containing resin layer of the filter obtained in Example 3, an ultraviolet cut filter (sharp cut filter SC
-39 (Fuji Photo Film Co., Ltd.) was laminated to produce a filter for plasma display panel having good light resistance.

In a xenon fade meter ("FAL-25AX-HC.B.EC" manufactured by Suga Test Instruments Co., Ltd.), an illuminance of 73,000 lux, a black panel temperature of 6
Under the conditions of 3 ° C. and a relative humidity of 33%, after exposure treatment for 80 hours using the ultraviolet absorbing layer as the exposed surface, the absorbance was measured with the same spectrophotometer as above, and the residual ratio of the dye was calculated from the value. 93.2% at 400 nm and 97. at 504 m.
It was 4% and 83.7% at 584 nm, and it was confirmed that the light resistance was excellent.

[0081]

INDUSTRIAL APPLICABILITY The display filter containing the tetraazaporphyrin dye, the dipyrazolylmethine dye and the dipyrazolyl squarylium dye of the present invention has a color tone without affecting the emission of the three primary colors of red, blue and green. It is a bright filter with good transmittance that can be adjusted, the color purity can be improved, the color temperature can be improved, and the durability is excellent such as heat resistance and light resistance.

[Brief description of drawings]

FIG. 1 is a light transmittance curve of a filter for a plasma display panel obtained in Example 1 of the present invention.

FIG. 2 is a light transmittance curve of the filter for plasma display panel obtained in Example 3 of the present invention.

Claims (3)

[Claims] 1. A tetraazaporphyrin dye represented by the following general formula (I), a dipyrazolylmethine dye represented by the following general formula (II), and a dipyrazolyl squarylium represented by the following general formula (III): A display filter characterized by containing a pigment. [Chemical 1] [In formula (I), R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an alkyl group which may have a substituent, a substituent An alkoxy group which may have an aryl group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent,
A dialkylamino group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent, and R ¹ and R ² ,
R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ may be connected to each other to form an aliphatic carbocycle. M represents two hydrogen atoms, a divalent metal atom, a trivalent mono-substituted metal atom, a tetravalent di-substituted metal atom or an oxy metal atom. ] [Chemical 2] [In the formula (II), R ⁹ represents an alkyl group which may have a substituent, an aryl group which may have a substituent or a hydrogen atom, and R ¹⁰ has a substituent. Optionally an alkyl group, an alkoxy group optionally having a substituent, an alkoxycarbonyl group optionally having a substituent, an aryl group optionally having a substituent, an aryloxy group, a substituent Represents an aryloxycarbonyl group which may have, an amino group which may have a substituent or a hydrogen atom, and R
¹¹ represents an alkyl group which may have a substituent, an aryl group which may have a substituent or a hydrogen atom, and X represents
Represents an oxygen atom or an NH group, and these R ¹⁰ , R ¹¹ and
And X may be different from each other between both pyrazole rings. ] [Chemical 3] [In the formula (III), R ¹² represents an alkyl group which may have a substituent, an aryl group which may have a substituent or a hydrogen atom, and R ¹³ has a substituent. Optionally an alkyl group, an alkoxy group optionally having a substituent, an alkoxycarbonyl group optionally having a substituent, an aryl group optionally having a substituent, an aryloxy group, a substituent An aryloxycarbonyl group which may have, an amino group which may have a substituent or a hydrogen atom,
Y represents an oxygen atom or an NH group, and these R ¹² ,
R ¹³ and Y may be different from each other between both pyrazole rings. ] 2. The display filter according to claim 1, further comprising an ultraviolet absorber-containing layer, wherein the ultraviolet absorber layer is outside of the dye-containing resin layer, that is, a display adhesive surface. A display filter characterized by being on the opposite side. 3. The display filter according to claim 1, wherein the display is a plasma display.