JP2000047025A - Blue filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a blue filter having high transmittance and high color purity by using a specified blue filter. SOLUTION: This filter has >2000 contrast ratio, and when the filter has 80% transmittance at 460 nm, it has <20% transmittance, preferably <10% at 545 nm and 610 nm. Further, the filter has >=30% residual rate of absorbance, preferably >=50% after the filter is irradiated with light from a xenon lamp for 100 hours, and it has >=30% residual rate, preferably >=50% of absorbance after heated at 200 deg.C for one hour. The contrast ratio is obtd. by interposing the produced filter between two polarizing plates, measuring the quantity of transmitted light under conditions of the polarizing axes of the two polarizing plates parallel to each other and perpendicular to each other, and calculating the ratio of the first light quantity to the second light quantity. The contrast ratio indicates the transparency of the filter. The contrast ratio of the filter is 3000 to 5000 when only the polarizing plates are used. By using the obtd. blue filter, a filter having extremely excellent light resistance and heat resistance and high durability can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blue filter.

The phthalocyanine compound used in the present invention has an absorption at 600 to 700 nm and is excellent in solvent solubility, light resistance, and heat resistance. ,
For example, when used in a color separation filter, a liquid crystal display color filter, an optical color filter, and the like used in an image pickup tube, an excellent effect is exhibited. The present invention exerts a very excellent effect particularly when used in a color filter for a liquid crystal display for blue.

[0003]

2. Description of the Related Art In recent years, liquid crystal display devices (LC)
D) is rapidly expanding its use in personal computers and word processors, as well as in car navigation systems and display devices for mobile phones, with the focus on full color and low cost, and the market continues to expand year by year. Color filters are indispensable for full color display.

In general, a color filter is formed by successively and repeatedly forming fine colored pixels of a thin film colored in a plurality of colors on a substrate such as glass, plastic, an image pickup device, a thin film transistor, and the like. Is provided. Various methods have been proposed for forming the colored pixels.

[0005] Dyes, which are constituents of color filters, can be broadly classified into pigments and dyes. Examples of the pigment-based production method include, for example, an acrylic resin, a pigment dispersion method using a coloring layer in which a pigment is dispersed in a polyimide resin or a poval resin, a printing method using an ink in which a pigment is dispersed in an epoxy resin, an acrylic method. An electrodeposition method using a colored layer in which a pigment is dispersed in a resin or an epoxy resin has been put to practical use. In addition, as a new method, a three-color film coated with a resist resin in which a pigment is dispersed is applied to a glass substrate, and a color filter is formed when peeled off, or a sol of pigment-dispersed silica is used. A method of selectively coloring a polysilane film by a sol-gel method has also been proposed. However, in any of the methods, since the dispersibility of the pigment in the resin is not sufficient, there have been problems in that the transmittance when formed into a color filter is insufficient and the contrast is poor.

On the other hand, in the dye system, a dyeing method of dyeing using a dyeable resin such as gelatin has been put into practical use. Although the dye system is superior in color to the pigment system, heat resistance and durability are high. The problem is that the chemical resistance is poor. Therefore, there is a need for a material that retains the color of a conventional dye and has high durability.

A phthalocyanine compound having a substituent is known as a dye having high durability and being soluble in a solvent. Examples of using a soluble phthalocyanine compound in a filter include JP-A-1-233401, JP-A-5-295283, and JP-A-9-171.
No. 108, etc., all of which are related to a dye for a green filter, and are different from the blue filter of the present invention. On the other hand, examples of using a soluble phthalocyanine compound for a blue filter include JP-A-8-179112, JP-A-8-302224, and JP-A-9-249814.

However, the filters using the phthalocyanine compounds disclosed in these publications have the disadvantage that the transmittance characteristics are insufficient for blue light and the color purity is poor.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve the above-mentioned drawbacks of the conventional blue filter, and to provide a blue filter having high transmittance and high color purity. To provide.

[0010]

The above objects are achieved by the following (1) to (7).

(1) When the contrast ratio is 2000 times or more and the transmittance at 460 nm is 80%, 545n
m and 610 nm are less than 20%, and the residual ratio of absorbance after irradiation with a xenon lamp for 100 hours is 30%.
A blue filter, wherein the residual ratio of absorbance after heating at 200 ° C. for 1 hour is 30% or more.

(2) The maximum absorption wavelength is 600 to 700 n
m, and a pyrolysis initiation temperature of 300 ° C. or higher, and a phthalocyanine compound soluble in a solvent.

(3) The blue filter according to (2), wherein the phthalocyanine compound is dissolved in a solvent in an amount of 1% by weight or more.

(4) The following general formula (1)

[0015]

Embedded image

[In the formula, at least two of R ^{1 to} R ¹⁶ are a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, the other is a hydrogen atom, and M is a divalent metal. Represents ]
The blue filter according to the above (2) or (3), comprising a phthalocyanine compound represented by the following formula:

(5) In the general formula (1),
R ¹ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹² , R ¹³ and R ¹⁶ are hydrogen atoms, R ² and R ³ , R ⁶ and R ⁷ , R ¹⁰ and R ¹¹ ,
A blue filter comprising the phthalocyanine compound according to the above (4), wherein at least one of the combinations of R ¹⁴ and R ¹⁵ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

(6) Any one of the above (2) to (5)
A blue filter comprising the phthalocyanine compound according to any one of the above, and a resin.

(7) The blue filter according to (6), wherein the resin is an acrylic resin.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The blue filter of the present invention has a contrast ratio of 2000 times or more and a transmittance of 545 nm and 610 nm of less than 20%, preferably less than 10% when a transmittance of 460 nm is 80%. The residual ratio of absorbance after irradiation with a xenon lamp for 100 hours is 30% or more, preferably 50% or more, and the residual ratio of absorbance after heating at 200 ° C. for 1 hour is 30% or more, preferably 50%.
The above is the feature. Here,
The contrast ratio is the ratio of the amount of transmitted light when the produced filter is sandwiched between two polarizing plates and the polarizing axes of the two polarizing plates are parallel and orthogonal. The contrast ratio is a measure of the transmittance of the filter, and the contrast ratio is 3000 to 5000 times when only the polarizing plate is used.
In a pigment-dispersed filter, since light is always scattered by pigment particles, the transmission efficiency decreases when the polarization axis is parallel, and the light blocking effect decreases when the polarization axis is orthogonal. As a result, the contrast ratio has not reached 1000 times. In contrast, the filter of the present invention has a contrast ratio of 20.
It has excellent transmission efficiency of 00 times or more. The color purity of the blue filter can be represented by a ratio of the transmittance at 460 nm to the transmittance at 545 nm and 610 nm. Therefore, for example, when the transmittance at 460 nm is 80% as in the blue filter of the present invention,
If the transmittance at 545 nm and 610 nm is less than 20%, especially less than 10%, it can be said that the color purity is high. In the present invention, since it has all the above characteristics, it has a sufficiently high transmittance and high color purity as a blue filter,
The present invention can provide a blue filter which retains a color equivalent to or higher than that of a conventional dye system in terms of color, has extremely excellent light resistance and heat resistance, and has high durability. Therefore, as a display material having absorption in the visible region in the field of optoelectronic information, for example, a material that exhibits excellent effects when used in a color separation filter used for an image pickup tube, a color filter for a liquid crystal display, a color filter for an optical device, and the like. is there. In particular, it exerts a very excellent effect when used for a color filter for blue liquid crystal display. In addition, a blue filter having all of the above characteristics can be actually manufactured by, for example, a method specifically described in each embodiment described later, but the blue filter is not limited thereto. Regardless of the manufacturing process, it goes without saying that a blue filter having all of the above characteristics is included in the technical scope of the present invention.

The blue filter according to the present invention has a maximum absorption wavelength of 600 to 700 nm, a thermal decomposition onset temperature of 300 ° C. or higher, and is soluble in a solvent, preferably 1
Characterized by comprising a phthalocyanine compound that dissolves in an amount of at least% by weight, more preferably a maximum absorption wavelength in a diethylene glycol dimethyl ether solvent in the range of 600 to 700 nm,
The solubility in diethylene glycol dimethyl ether is 2% by weight or more, and the thermal decomposition onset temperature is 300 ° C.
It is characterized by comprising the phthalocyanine compound described above. With such a blue filter, 60
Since it contains a phthalocyanine compound having excellent absorption at 0 to 700 nm and excellent solvent solubility and heat resistance, sufficient dispersibility in resins and the like is obtained, and excellent transmittance and color purity as a blue filter are obtained. The present invention can provide a blue filter having high transmittance, high color purity, high contrast, and excellent durability.

The pyrolysis onset temperature referred to herein is measured by a differential thermal-thermogravimetric simultaneous measuring device (DAT-TGA),
It was defined as the temperature at which the degree of thermogravimetric loss per ° C became 0.3% by weight / ° C or more.

The blue filter of the present invention also preferably comprises a phthalocyanine compound produced in a benzonitrile solvent. It is preferable to produce the phthalocyanine compound in a benzonitrile solvent because the purity is high, and as a result, a phthalocyanine compound having high solubility in a solvent or a resin used in preparing a filter is obtained. As a method for producing a phthalocyanine compound in a benzonitrile solvent, a known general method can be used. That is,
A Wyler method produced by reacting urea with a metal salt in the presence of a condensed acid using phthalic anhydride or phthalic anhydride as a raw material, a phthalonitrile method produced by reacting phthalonitrile with a metal salt, and the like. In addition, it can also be produced using phthalic acid, phthalic diamide, 1,3-diiminoisoindoline and derivatives thereof as raw materials. Of these, the phthalonitrile method using phthalonitrile as a raw material is preferred. When manufacturing by a phthalonitrile method, a metal compound and phthalonitrile are reacted in a benzonitrile solvent at a reaction temperature of 30 to 300 ° C, preferably 80 ° C.
It is preferably carried out at a temperature of up to 200 ° C.

The blue filter according to the present invention further has the following general formula (1):

[0025]

Embedded image

[In the formula, at least two of R ^{1 to} R ¹⁶ are a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, the other represents a hydrogen atom, and M is a divalent metal. Represents ]
And a phthalocyanine compound represented by the formula: In the phthalocyanine compound having such a chemical structural formula, 600-700
Because it has absorption in nm, and has excellent properties of solvent solubility, light resistance, and heat resistance, it is used as a display material having absorption in the visible region in the field of optoelectronic information, for example, a color separation filter used in an image pickup tube, a liquid crystal. It exerts a very excellent effect when used for a display color filter, an optical color filter and the like, particularly for a blue liquid crystal display color filter.

In the general formula (1), at least two, preferably 3 to 6, of R ^{1 to} R ¹⁶ are a straight-chain or branched chain having 1 to 20, preferably 3 to 8 carbon atoms. , A cyclic alkyl group. Specifically, for example, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, iso-butyl, tert-butyl, cyclobutyl, n-pentyl, sec-pentyl, iso-pentyl, tert-pentyl , N
eo-pentyl, 3-pentyl, cyclopentyl, 2-methylbutyl, n-hexyl, iso-hexyl, sec-hexyl, 3-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, tert-octyl, and the like. Can be.

In the general formula (1), M is a divalent metal, specifically, iron, magnesium, nickel,
Cobalt, copper, palladium, zinc and the like can be mentioned. Preferred are cobalt, copper, zinc and nickel, and particularly preferred is zinc.

Among the phthalocyanine compounds represented by the general formula (1), R ¹ , R ⁴ , R ⁵ , R ⁸ ,
R ⁹ , R ¹² , R ¹³ , and R ¹⁶ are hydrogen atoms, and at least one of the combinations of R ² and R ³ , R ⁶ and R ⁷ , R ¹⁰ and R ¹¹ , and R ¹⁴ and R ¹⁵ has 1 to 1 carbon atoms. 20, preferably a phthalocyanine compound which is a straight-chain, branched-chain or cyclic alkyl group having 3 to 8 carbon atoms, particularly preferably the following general formula (2)

[0030]

Embedded image

[Wherein, R represents a linear, branched or cyclic alkyl group having 3 to 8 carbon atoms, and M represents a divalent metal. ]. Specifically, for example, phthalocyanine compounds (1) to (2)
0).

[0032]

[Table 1]

Specific production examples of the phthalocyanine compounds shown in Table 1 above are shown below for the phthalocyanine compounds (1) and (2).

Production Example of Phthalocyanine Compound (1) In a 100 ml four-necked flask, 15.00 g (50 mmol) of 4-t-butylphthalonitrile, zinc iodide 7.
80 g (24 mmol) and benzonitrile 60 m
and then reacted under reflux for 8 hours. After completion of the reaction, benzonitrile was distilled off, and the residue was washed twice with 500 ml of methanol to obtain 12.54 g of a target blue cake (yield: 76.8%).

Visible absorption spectrum Maximum absorption wavelength 674 nm (ε = 2.42 × 10 ⁵ ) in diethylene glycol methyl ether Thin film 682 nm Solubility 9% by weight based on ethylene glycol dimethyl ether Thermal decomposition onset temperature 516 ° C. Production example of phthalocyanine compound (2) 100 ml In a one-necked flask, 15.00 g (50 mmol) of 4-t-butylphthalonitrile, copper (I) chloride
2.42 g (24 mmol) and benzonitrile 6
0 ml was charged and reacted under reflux for 8 hours. After the completion of the reaction, benzonitrile was distilled off, and the resultant was washed twice with 500 ml of methanol to obtain a blue cake (11.78).
g was obtained (72.3% yield).

Maximum absorption wavelength of visible absorption spectrum 674 nm (ε = 1.87 × 10 ⁵ ) in ethylene glycol methyl ether Thin film 631 nm Solubility 2.5% by weight based on ethylene glycol methyl ether Thermal decomposition start temperature 517 ° C. Using the above-mentioned phthalocyanine compound As a method of producing a color filter for LCD or a color separation filter for an image pickup tube, which is one embodiment of the blue filter of the present invention,
A film is formed on a substrate using a photosensitive resin or a photopolymerizable monomer by casting, spin coating, or the like, and after patterning by light irradiation, the resin layer is dipped with a dye (including at least the above-described phthalocyanine compound, the same applies hereinafter). A dye layer by dry etching or a lift-off method, or by dissolving or dispersing a dye in a photosensitive resin or a photopolymerizable monomer in advance, and casting or spin coating on a substrate. A method of forming a film and patterning by light irradiation, a method of patterning by a printing method, and the like can be given.

The resin that can be used for the blue filter of the present invention is not particularly limited, and any known resin that has been developed as a resin material for a blue filter can be used. For example, polyamide resin, polyester resin, polycarbonate resin, polyether resin, polyolefin resin, polysulfone resin, polystyrene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, ethylene-vinyl acetate copolymer, acrylic Resin, ionomer resin, polyphenylene sulfide resin, styrene copolymer resin, fluorine resin, phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, alkyd resin, polyimide resin, polyurethane resin, A xylene resin or the like can be used alone or as a mixture. Among these resins, when the above-mentioned phthalocyanine compound is used, an acrylic resin is preferable. By using the acrylic resin, the solubility of the phthalocyanine compound in the resin is increased, and as a result, a highly transparent resin composition containing the phthalocyanine compound at a high concentration can be provided. As a result, the light resistance and the absorption wavelength of the resin composition are more effectively controlled.

As the acrylic resin, a resin whose monomer and oligomer are composed of the following compounds is preferable. That is, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
2-hydroxypropyl methacrylate, acrylamide, methacrylamide, N-hydroxymethylacrylamide, polyethylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, styrene, vinyl acetate, various acrylic esters, various Examples include methacrylic acid ester, acrylonitrile, dipentaerythritol hexaacrylate, hexaacrylate of caprolactone adduct of dipentaerythritol hexaacrylate, melamine acrylate, epoxy acrylate prepolymer and the like. Among them, in particular, acrylic resins composed of (meth) acrylic acid, hydroxyalkyl (meth) acrylate, various alkyl (meth) acrylates, composed of (meth) acrylic acid, hydroxyalkyl (meth) acrylate, various alkyl (meth) acrylates, and styrene An acrylic resin composed of an acrylic resin, (meth) acrylic acid, and various alkyl (meth) acrylates is preferable.

Specific examples of preferred acrylic resins include the following. Resin (1) Resin having the following monomer composition and having a weight average molecular weight of 10,000 to 100,000: Styrene 5 mol% 22-hydroxyethyl methacrylate 22 mol% Ethyl methacrylate 54 mol% Methacrylic acid 19 mol% Resin (2) The following monomer composition Resin having a weight average molecular weight of 10,000 to 100,000 styrene 62 mol% ethylene glycol monoethyl ether acrylate 32 mol% acrylic acid 6 mol% resin (3) methacrylic acid having a weight average molecular weight of 10,000 to 100,000 having the following monomer composition Benzyl 70 mol% Methacrylic acid 30 mol% Specific production examples thereof are shown below. In the following production examples, “parts” means “parts by weight” unless otherwise specified.

Production Example of Resin (1) In a 1-liter four-necked flask, 175.0 parts of diethylene glycol dimethyl ether, 8.8 parts of styrene, 43.8 parts of 2-hydroxyethyl methacrylate, 26.3 parts of methacrylic acid, 96.3 parts of ethyl methacrylate were charged and heated to 90 ° C., and 145.0 parts of diethylene glycol dimethyl ether, 8.8 parts of styrene, 43.8 parts of 2-hydroxyethyl methacrylate, 26.3 parts of methacrylic acid and 26.3 parts of methacrylic acid were prepared in advance. A mixture obtained by mixing and dissolving 96.3 parts of ethyl and 2.92 parts of Niper BMT (manufactured by NOF Corporation) was dropped in 3 hours, and reacted at 90 ° C. for 3 hours. Further, a solution prepared by dissolving 1.75 parts of Niper BMT in 10 parts of diethylene glycol dimethyl ether was added, and the reaction was continued for 1 hour to obtain a diethylene glycol dimethyl ether solution of the resin (1).

Production Example of Resin (2) Cellosolve acetate 17 was placed in a 1-liter four-necked flask.
5.0 parts, 113.8 parts of styrene, 19.6 parts of diethylene glycol monoethyl ether acrylate, and 41.3 parts of acrylic acid were charged and heated to 90 ° C., and 175.0 parts of cellosolve acetate and 113.8 parts of styrene were previously prepared. ,
19.6 parts of diethylene glycol monoethyl ether acrylate and 41.3 parts of acrylic acid and Niper BM
A mixture obtained by mixing and dissolving 2.92 parts of T (manufactured by NOF Corporation) was dropped in 3 hours, and reacted at 90 ° C. for 3 hours. Further, a solution obtained by dissolving 1.75 parts of Niper BMT in 10 parts of diethylene glycol dimethyl ether was added,
The reaction was continued for one hour to obtain a cellosolve acetate solution of the resin (2).

Production Example of Resin (3) Cellosolve acetate 17 was placed in a 1-liter four-necked flask.
5.0 parts, 144.7 parts of benzyl methacrylate and 30.3 parts of methacrylic acid were charged and heated to 90 ° C., and 175.0 parts of cellosolve acetate and benzyl methacrylate were added in advance.
4.7 parts, 30.3 parts of methacrylic acid and Niper BM
A mixture of 2.92 parts of T (manufactured by NOF Corporation) was dissolved in 3
The reaction was carried out at 90 ° C. for 3 hours. further,
A solution obtained by dissolving 1.75 parts of Niper BMT in 10 parts of diethylene glycol dimethyl ether was added, and the reaction was continued for 1 hour to obtain a cellosolve acetate solution of the resin (3).

Since the phthalocyanine compound used in the blue filter of the present invention has high solubility in a resin, a resin having a higher molecular weight than that of the conventional one can be used. Specifically, a high molecular weight resin of 30,000 or more, for example, about 100,000 to 200,000 can be used. In a conventional color filter in which a pigment is dispersed in a resin, the molecular weight of the resin used is limited to about tens of thousands in view of the dispersibility of the pigment. Therefore, there is a problem in the heat resistance and solvent resistance of the obtained color filter, and it is necessary to increase the amount of the crosslinking agent with respect to the resin or to use a special crosslinking agent. On the other hand, in the phthalocyanine compound used for the blue filter of the present invention, by combining with a high molecular weight resin, the amount of the crosslinking agent is increased, and the heat resistance and the solvent resistance are excellent without using a special crosslinking agent. It is possible to produce a blue filter.

The resin contained in the blue filter of the present invention is preferably a photosensitive resin.

As the photosensitive resin, any resin composition may be used as long as it undergoes a chemical reaction by the action of light, resulting in a change in solubility or affinity for a solvent or a change from a liquid to a solid. , Aromatic diazonium salt resin, o-quinonediazide resin, bisazide resin, photodegradable photosensitive resin such as polysilane, photodimerized photosensitive resin such as cinnamic acid resin, unsaturated polyester resin, epoxy acrylate Photopolymerization-type photosensitizers such as prepolymers such as urethane acrylate or polyvinyl alcohol as a binder polymer, polyamide, polymethacrylate, etc. and various acrylate or methacrylate monomers and a photopolymerization initiator. Resins, of which photopolymerizable Light resin is preferable. In particular, the binder polymer is an acrylic resin, and a resin composed of various (meth) acrylate monomers and a photopolymerization initiator is preferable. Examples of the photopolymerization initiator in the photosensitive resin include a benzoin alkyl ether compound, an acetophenone compound, a benzophenone compound, a phenyl ketone compound, a thioxanthone compound, and an anthraquinone compound.

Specific preferred examples of the photosensitive resin include:
For example, the following are mentioned.

Blending composition of photosensitive resin (1) Binder resin Resin (1) 61 parts Monomer Trimethylol perfluorotrimethacrylate 36 parts Photopolymerization initiator Irgacure 907 4 parts Blending composition of photosensitive resin (2) Binder resin Resin ( 2) 57 parts Monomer Pentaerythritol tetraacrylate 41 parts Photopolymerization initiator 4- (pN, N-diethoxycarbonylethyl-2,6-di (trichloromethyl) -s-triazine) 2 parts Photosensitive resin (3) Blending composition Binder resin Resin (3) 57 parts Monomer Pentaerythritol tetraacrylate 41 parts Photopolymerization initiator 4- (pN, N-diethoxyethoxycarbonylethyl-2,6-di (trichloromethyl) -s-triazine) 2 parts These For the photosensitive resin, a monomer and a photopolymerization initiator are added to the solution of the corresponding binder resin. Acceleration and lysed, after a uniform solution can be prepared by evaporating the solvent.

The pigment for a blue filter of the present invention may be mixed with known pigments and dyes in addition to the phthalocyanine compound, if necessary.

The pigment includes, for example, inorganic pigments such as ultramarine blue and navy blue, and organic pigments represented by a color index (CI) number below.

Examples of the violet pigment include C.I.
I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 2
9, C.I. I. Pigment Violet 30, C.I. I. Pigment Violet 37, C.I. I. Pigment Violet 40 and C.I. I. Pigment Violet 50
And the like.

Examples of the blue pigment include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:
6, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60 and C.I. I. Pigment Blue 64 and the like.

Examples of the dye include C.I. I. Acid Blue 29, C.I. I. Disperse Blue 165, C.I.
I. Azo dyes such as Basic Blue 41, C.I. I.
Bat Blue 4, C.I. I. Acid Blue 40, C.I.
I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse Blue 56, C.I. I.
Anthraquinone dyes such as Disperse Blue 60,
C. I. Indigo dyes such as Pad Blue 5, C.I.
I. Phthalocyanine dyes such as Direct Blue 86; I. Basic Blue 3, C.I. I. Examples thereof include quinone imine dyes such as Basic Blue 9.

The method for producing the resin composition containing the dye (the dye contains at least the phthalocyanine compound), which is the main raw material of the blue filter of the present invention, is not particularly limited, and examples thereof include the following methods. Can be

(1) A method in which the above phthalocyanine compound is used alone or mixed with another dye, and then mixed with a thermoplastic resin melted by heating.

(2) A method in which the above phthalocyanine compound is used alone or mixed with another dye, dissolved in a solvent together with a resin, mixed, and then the solvent is volatilized.

(3) A method in which the above phthalocyanine compound is used alone or mixed with another dye, mixed with a polymerizable vinyl compound which is a precursor of a resin, and the mixed solution is polymerized to produce the phthalocyanine compound.

The present invention is particularly useful when the blue filter constituting the color filter is formed by using a resin composition containing a blue colorant containing the phthalocyanine compound as a colored resist. The present inventors have found that the present invention can exert an excellent effect of solving all of the technical problems that the company has.

The method for producing the blue filter of the present invention is not particularly limited, and a conventionally proposed pigment-based production method can be applied. Since the phthalocyanine compound contained in the blue filter of the present invention has high solubility in a resin, it can produce a high-contrast blue filter having transparency when applied to any of the methods.

In the conventional method for producing a blue filter constituting a color filter (the process for producing a blue filter in the method for producing a color filter), the following method is particularly mentioned as a method for applying the phthalocyanine compound.

(1) A resist is formed using a resin composition containing a blue colorant containing the phthalocyanine compound,
This is applied to a transparent substrate, exposed and developed to form a blue colored pattern among the three primary colors. Regarding red and green, a color filter can be obtained by forming the three colored patterns by repeating the same process operation as the blue colored pattern using the resin composition containing the red and green dyes, respectively. Will be.

(2) A method of obtaining a blue colored pattern by etching a polyimide resin composition containing a blue colorant containing the phthalocyanine compound.

(3) A method of forming a color pattern directly on a glass substrate by an offset printing machine using the epoxy resin composition containing a blue colorant containing the phthalocyanine compound as a coloring ink. For red and green, the color filter is formed by forming the three color patterns by repeating the same process operation as the blue color pattern using the epoxy resin composition containing the dyes for red and green, respectively. Will be obtained.

(4) An ITO electrode patterned into a predetermined shape on a glass substrate is used as one electrode and immersed in an electrodeposition solution made of a resin composition containing a blue dye containing the phthalocyanine compound to form a blue color on the electrode. Of forming a blue colored pattern by depositing a colored film. Regarding red and green, a color filter can be obtained by forming a three-color pattern by repeating the same process operation as a blue coloring pattern using a resin composition containing a red and green colorant, respectively. become.

In addition to the above-mentioned conventional methods (1) to (4), the present invention can also be applied to the following method proposed as a novel manufacturing method.

(5) A method of forming a blue film by applying a resist resin in which a blue dye containing the phthalocyanine compound is dispersed. The red and green dyes are also coated with a resist resin in which the respective dyes are dispersed to form red and green films, and the three color films are attached to a glass substrate and peeled off to obtain a color filter. Will be done.

(6) A method of selectively coloring a polysilane film by a sol-gel method using a sol of colored silica containing a blue dye containing a phthalocyanine compound.

In the above method (1), the dye layer can be patterned on an optically transparent substrate. As the substrate to be used, the dye layer can be patterned. There is no particular limitation as long as it has the function of For example, glass plate, polyvinyl alcohol, hydroxyethyl cellulose, methyl methacrylate, polyester, butyral, polyamide, polyethylene, vinyl chloride, vinylidene chloride, polycarbonate, polyolefin copolymer resin, vinyl chloride copolymer resin, vinylidene chloride copolymer resin, styrene copolymer A resin film or plate such as a resin may be used. It is also possible to form a patterned dye layer integrally with a dye applied as a color filter.

[0068]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 5 g of the phthalocyanine compound (1) shown in Table 1 was dissolved in 25 g of a solution of the photosensitive resin (1) in diethylene glycol dimethyl ether (nonvolatile content: 20%), and the solvent was applied to a glass substrate by a spin coater. 2μm thickness after drying
Was spin-coated so that Next, after prebaking at 60 ° C. for 20 minutes, exposure was performed using a photomask for pattern formation. After developing with a 1% aqueous sodium carbonate solution and washing with pure water, post-baking was performed at 200 ° C. for 10 minutes to produce a blue color filter.

The depolarization (= depolarization) characteristics, transmittance characteristics, light fastness and heat resistance of this color filter were evaluated. The results are shown in Table 2.

Example 2 Example 1 was repeated except that the phthalocyanine compound (2) was used in place of the phthalocyanine compound (1) and the photosensitive resin (2) was used instead of the photosensitive resin (1). A blue color filter was produced in the same manner as described above. The depolarization characteristics, transmittance characteristics, light resistance and heat resistance of this color filter were evaluated. The results are shown in Table 2.

Example 3 Example 1 was repeated except that the phthalocyanine compound (3) was used instead of the phthalocyanine compound (1) and the photosensitive resin (3) was used instead of the photosensitive resin (1). A blue color filter was produced in the same manner as described above. The depolarization characteristics, transmittance characteristics, light resistance and heat resistance of this color filter were evaluated. The results are shown in Table 2.

Example 4 A blue color filter was produced in the same manner as in Example 1 except that the phthalocyanine compound (5) was used instead of the phthalocyanine compound (1). The depolarization characteristics, transmittance characteristics,
Light resistance and heat resistance were evaluated. The results are shown in Table 2.

Example 5 A blue color filter was produced in the same manner as in Example 1, except that the phthalocyanine compound (13) was used instead of the phthalocyanine compound (1). The depolarization characteristics, transmittance characteristics, light resistance and heat resistance of this color filter were evaluated. The results are shown in Table 2.

Example 6 Example 1 was repeated except that the phthalocyanine compound (17) was used in place of the phthalocyanine compound (1) and the photosensitive resin (2) was used instead of the photosensitive resin (1). A blue color filter was produced in the same manner as described above. The depolarization characteristics, transmittance characteristics, light resistance and heat resistance of this color filter were evaluated. The results are shown in Table 2.

The evaluation of the depolarization characteristics was performed by the following method. The sample of the produced color filter was sandwiched between two polarizing plates, and the ratio of the amount of transmitted light (contrast ratio) when the polarizing axes of the two polarizing plates were parallel and orthogonal was measured. The following two-stage evaluation was performed based on the measurement results. ：: Contrast ratio of 2000 times or more ×: Contrast ratio of less than 2000 times As for the transmittance characteristics, the transmittance of the sample in the range of 400 to 700 nm was measured, and the following three stages were evaluated based on the measurement results. ：: When the transmittance at 460 nm is 80%, the transmittance at 545 nm and 610 nm is less than 10% Δ: When the transmittance at 460 nm is 80%, the transmittance at 545 nm and 610 nm is 10 or more to less than 20% X: when the transmittance at 460 nm is 80%, the transmittance at 545 nm and 610 nm is 20% or more. However, when the transmittance of the sample is measured and the transmittance at 460 nm deviates from 80%. , 80%, and 545 nm and 61 when converted.
Judgment was made from the numerical value of the transmittance at 0 nm.

The light fastness was measured by setting the sample in a xenon light fastness tester (irradiation amount: 100,000 lux).
The following three grades were evaluated based on the residual ratio of absorbance at the maximum absorption wavelength in the range of ~ 700 nm. ：: Residual rate of absorbance after 100 hours passed 80% or more △: Residual rate of absorbance after 100 hours passed 30% or more to 8
Less than 0% ×: Residual rate of absorbance after 100 hours has passed Less than 30% The heat resistance is as follows: Residual rate of absorbance at the maximum absorption wavelength in the range of 400 to 700 nm after heating the sample at 200 ° C. for 1 hour with a hot air dryer. The following three-step evaluation was performed. ：: Residual rate of absorbance of 80% or more △: Residual rate of absorbance of 30% or more to less than 80% ×: Residual rate of absorbance of less than 30%

[0078]

[Table 2]

[0079]

According to the invention of the blue filter of the present invention, when the contrast ratio is 2000 times or more and the transmittance at 460 nm is 80%, the transmittance at 545 nm and 610 nm is less than 20%, preferably less than 10%. Yes, the residual ratio of absorbance after irradiation with a xenon lamp for 100 hours is 30%
Or more, preferably 50% or more, and the residual ratio of absorbance after heating at 200 ° C. for 1 hour is 30% or more, preferably 50% or more.
%, It has extremely excellent depolarization characteristics, high transmittance and high color purity enough for a blue filter, and retains a color equivalent to or higher than conventional dyes in terms of color. Further, it is possible to provide a blue filter having extremely excellent light resistance and heat resistance and high durability. Therefore, as a display material having absorption in the visible region in the field of optoelectronic information, for example, a material that exhibits excellent effects when used in a color separation filter used for an image pickup tube, a color filter for a liquid crystal display, a color filter for an optics, and the like. is there. In particular, it exerts a very excellent effect when used for a color filter for blue liquid crystal display.

The blue filter of the present invention is characterized in that it has a maximum absorption wavelength of 600 to 700 nm, a thermal decomposition onset temperature of 300 ° C. or higher, and contains a phthalocyanine compound soluble in a solvent. , 600-7
Since it contains a phthalocyanine compound having excellent absorption at 00 nm and excellent solvent solubility and heat resistance, sufficient dispersibility in resins and the like is obtained, and excellent transmittance, color purity and contrast as a blue filter are obtained. And a blue filter having high transmittance and high color purity, which has excellent durability. Further, particularly in the present invention, a phthalocyanine compound having a maximum absorption wavelength in a diethylene glycol dimethyl ether solvent in the range of 600 to 700 nm, a solubility in diethylene glycol dimethyl ether of 2% by weight or more, and a thermal decomposition initiation temperature of 300 ° C. or more. The effect is more remarkable (including the peak effect), and has extremely excellent depolarization characteristics, transmittance characteristics, light resistance and heat resistance. Accordingly, as a display material having absorption in the visible region in the field of optoelectronic information, for example, a color separation filter used for an image pickup tube, a color filter for liquid crystal display, a color filter for optical use, and particularly used for a color filter for blue liquid crystal display. In this case, it has a very excellent effect.

The invention of the blue filter of the present invention is characterized in that the phthalocyanine compound described in the invention of the blue filter is dissolved in a solvent in an amount of 1% by weight or more. The degree (including the peak effect) is more pronounced. Further, if the phthalocyanine compound is produced in a benzonitrile solvent, the purity is high, and a high solubility in the solvent or resin used in preparing the filter can be obtained. The degree of action and effect (peak effect) obtained by the invention of (1) is more remarkable.

The invention of the blue filter of the present invention is characterized by containing the phthalocyanine compound represented by the above general formula (1). Depending on the material, it has absorption in the range of 600 to 700 nm, and has excellent properties of solvent solubility, light resistance, and heat resistance. It exerts a very excellent effect when used for a decomposition filter, a liquid crystal display color filter, an optical color filter, and the like, particularly for a blue liquid crystal display color filter.

According to the invention of the blue filter of the present invention, R ¹ , R ⁴ , R ⁵ , R ⁸ ,
R ⁹ , R ¹² , R ¹³ , and R ¹⁶ are hydrogen atoms, and at least one of the combinations of R ² and R ³ , R ⁶ and R ⁷ , R ¹⁰ and R ¹¹ , and R ¹⁴ and R ¹⁵ has 1 to 1 carbon atoms. Since the phthalocyanine compound described in the invention of the blue filter, which is 20 linear, branched, or cyclic alkyl groups, is contained, the degree of the effect obtained by the invention of the blue filter (peak effect) Is very remarkable.

The blue filter of the present invention comprises the phthalocyanine compound according to any one of the above-mentioned blue filters and a resin. In addition to the resulting effects, the use of resin as a display material having absorption in the visible region in the field of optoelectronic information, such as color separation filters used in image pickup tubes, color filters for liquid crystal displays, color filters for optics, etc. In particular, it is extremely excellent in workability, moldability, workability, and the like when used for a color filter for a liquid crystal display for blue.

In the invention of the blue filter of the present invention, since the acrylic resin is used, the solubility of the phthalocyanine compound in the resin is increased, and as a result, a resin composition containing the phthalocyanine compound at a high concentration and having high transparency is obtained. Can be provided. As a result, the phthalocyanine compound (dye) -containing resin composition, which is the main raw material of the blue filter, has a better effect on controlling the light resistance and the absorption wavelength.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AB13 CB13 CC13 2H048 CA04 CA14 CA19 2H091 FA02Y FB02 FB04 FD24 LA12 LA15 LA17

Claims (7)

[Claims] 1. When the contrast ratio is 2000 times or more and the transmittance at 460 nm is 80%, the transmittance at 545 nm and 610 nm is less than 20%, and the residual ratio of absorbance after irradiation with a xenon lamp for 100 hours is 30. %, And the residual ratio of absorbance after heating at 200 ° C. for 1 hour is 3%.
A blue filter characterized by being at least 0%. 2. A blue filter having a maximum absorption wavelength of 600 to 700 nm, a thermal decomposition onset temperature of 300 ° C. or higher, and comprising a phthalocyanine compound soluble in a solvent. 3. The blue filter according to claim 2, wherein the phthalocyanine compound is dissolved in a solvent in an amount of 1% by weight or more. 4. The following general formula (1): [Wherein at least two of R ^{1 to} R ¹⁶ have 1 to 1 carbon atoms.
20 are linear, branched or cyclic alkyl groups, the others represent hydrogen atoms, and M represents a divalent metal. The blue filter according to claim 2, comprising a phthalocyanine compound represented by the following formula: 5. In the general formula (1), R ¹ ,
R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹² , R ¹³ , and R ¹⁶ are hydrogen atoms, and R ² and R ³ , R ⁶ and R ⁷ , R ¹⁰ and R ¹¹ , R ¹⁴ and R ¹⁵ At least one of the combinations has 1 to 1 carbon atoms.
A linear, branched or cyclic alkyl group of 20.
A blue filter comprising the phthalocyanine compound according to item 1. 6. A blue filter comprising the phthalocyanine compound according to claim 2 and a resin. 7. The blue filter according to claim 6, wherein the resin is an acrylic resin.