JP2010191468A - Color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter being high in contrast, excellent in light fastness, and wide in color reproducing area; and to provide a liquid crystal display device capable of reproducing clear-cut and bright colors. <P>SOLUTION: The color filter includes at least a red-colored filter segment, a green-colored filter segment, a blue-colored filter segment, a yellow-colored filter segment, and the NTCS ratio is 94 to 125%. The yellow-colored filter segment is formed by using a yellow-colored composition for a color filter containing at least one or more yellow pigment selected from groups consisting of C.I.Pigment Yellow 139, 150 and 185, transparent resin, and a pigment carrier made of the precursors or a mixture of them. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a color liquid crystal display device, a color filter used for a color image pickup tube element and the like, and a liquid crystal display device.

  In recent years, liquid crystal display devices have been applied in TV monitor applications, personal computer monitor applications, mobile applications, etc., and for color filters used there, lightness, color purity, and coating for forming each color filter segment are used. The required level for various properties such as uniformity, sensitivity, developability, and pattern shape is increasing. Furthermore, since color filters are used for a long period of time, there is a strong demand for quality such as heat resistance and light resistance. In particular, with the widespread use of liquid crystal display devices, there is a strong demand for improving contrast and expanding the color reproduction region because it can express vivid and vivid colors.

Patent Document 1 specifies CIE label values of x, y, and Y for filter segments of red, green, and blue colors that constitute a color filter, and specifies pigment selection, mixing ratio, particle size, and the like. A method of realizing a good color reproduction region with high brightness is disclosed.
Patent Document 2 discloses a method for expanding a color reproduction region by adding a cyan filter segment having a specific CIE label value to a red filter segment, a green filter segment, and a blue filter segment.
However, in any of the above methods, the expansion of the color reproduction region of the liquid crystal display device is insufficient, and a liquid crystal display device that is superior in color reproducibility is required.

Japanese Patent Laid-Open No. 10-186124 JP 2005-49791 A

  Accordingly, an object of the present invention is to provide a color filter having high contrast, excellent light resistance, a wide color reproduction region, and a liquid crystal display device capable of expressing sharp and vivid colors.

  The color filter of the present invention includes a red filter segment, a green filter segment, a blue filter segment, and a yellow filter segment. I. A yellow coloring composition comprising at least one yellow pigment selected from the group consisting of Pigment Yellow 139, 150 and 185, a pigment dispersant, and a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof. It is characterized by being formed using.

  Furthermore, the liquid crystal display device of the present invention is a liquid crystal display device comprising the color filter of the present invention and a pseudo white LED light source formed by applying a phosphor on the surface of a blue LED, the pseudo white color The LED light source has a wavelength λ1 at which the emission intensity is maximum within a wavelength range of 430 nm to 485 nm, a peak wavelength λ2 of the emission intensity within a wavelength range of 530 nm to 580 nm, and a wavelength with respect to the emission intensity I1 at the wavelength λ1. It has a spectral characteristic in which the ratio I2 / I1 of the emission intensity I2 at λ2 is 0.2 or more and 0.7 or less.

  The liquid crystal display device of the present invention is a liquid crystal display device comprising the color filter of the present invention and a cold cathode fluorescent tube light source, wherein the cold cathode fluorescent tube light source emits light within a wavelength range of 470 nm to 530 nm. It has a wavelength λ3 where the intensity is maximum, a wavelength λ4 where the emission intensity is maximum in the wavelength range of 530 nm to 580 nm, and the ratio I3 / I4 of the emission intensity I3 at the wavelength λ3 to the emission intensity I4 at the wavelength λ4 Has a spectral characteristic of 0.2 or more and 0.7 or less.

  The liquid crystal display device of the present invention is a liquid crystal display device comprising the color filter of the present invention and a three-color LED light source, and the three-color LED light source has a light emission intensity within a wavelength range of 430 nm to 485 nm. The wavelength λ5 is the maximum, the wavelength λ6 has the maximum emission intensity in the wavelength range of 530 nm to 580 nm, and the ratio I6 / I5) of the emission intensity I6 at the wavelength λ6 to the emission intensity I5 at the wavelength λ5 is It has a spectral characteristic of 0.2 or more and 0.7 or less.

  A red filter segment, a green filter segment, a blue filter segment and a yellow filter segment, wherein the yellow filter segment comprises C.I. I. A yellow coloring composition comprising at least one yellow pigment selected from the group consisting of Pigment Yellow 139, 150 and 185, a pigment dispersant, and a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof. The color filter of the present invention formed by using the panel has a wide color reproduction region of the panel and has excellent light resistance.

It is a schematic sectional drawing of the color liquid crystal display device which can apply the color filter of this invention. It is a perspective view which shows the backlight unit used for the color liquid crystal display device shown in FIG. It is a conceptual diagram of the apparatus which measures contrast ratio. It is the figure which showed the emission spectrum of the pseudo white LED light source, the cold cathode fluorescent tube light source, and the three-color LED light source.

First, the cyan coloring composition will be described.
The cyan coloring composition for color filters of the present invention comprises (i) C.I. I. Pigment Blue 15: 3 and C.I. I. A phthalocyanine-based blue pigment containing one or both of Pigment Blue 15: 4; and (ii) C.I. I. A phthalocyanine-based green pigment containing Pigment Green 7; and (iii) a pigment carrier made of a transparent resin, a precursor thereof, or a mixture thereof. Note that C.I. I. Means a color index.

  (I) The phthalocyanine blue pigment is C.I. I. Pigment Blue 15: 3 and C.I. I. Pigment Blue 15: 4, or both of them may be included, but other phthalocyanine-based blue pigments may also be included. Other phthalocyanine blue pigments include C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 75 or the like can be used.

  C. I. Pigment Blue 15: 3 and / or C.I. I. It is preferable that Pigment Blue 15: 4 occupies 20 to 100% by weight of the total weight of the phthalocyanine blue pigment in total. C. I. Pigment Blue 15: 3 and / or C.I. I. When the ratio of Pigment Blue 15: 4 to the total phthalocyanine-based blue pigment is less than 20% by weight, the color reproduction region obtained becomes narrow when paneled, and this is not preferable because the light resistance is deteriorated.

The (ii) phthalocyanine green pigment is C.I. I. Pigment Green 7 may be included, but other phthalocyanine green pigments may also be included. Other phthalocyanine green-blue pigments include C.I. I. Pigment Green 36.
C. I. Pigment Green 7 preferably accounts for 20 to 100% by weight of the total weight of the phthalocyanine green pigment. C. I. When the ratio of Pigment Green 7 to the total phthalocyanine-based green pigment is less than 20% by weight, it is not preferable from the viewpoint that the color reproduction region obtained becomes narrow when paneled.

  In the cyan coloring composition for a color filter of the present invention, (i) phthalocyanine blue pigment and (ii) phthalocyanine green pigment are in a weight ratio of 1:99 to 99: 1, preferably 3:97 to 97: 3. More preferably, it is contained in a ratio of 5:95 to 95: 5. (I) When the blending amount of the phthalocyanine blue pigment is out of the above range, the color reproduction region is not sufficiently expanded, which is not preferable.

  A mixture containing at least one of the (i) phthalocyanine blue pigment and (ii) phthalocyanine green pigment containing a water-soluble organic solvent that does not substantially dissolve the pigment, the water-soluble inorganic salt, and the water-soluble inorganic salt. After kneading (hereinafter, this process is referred to as salt milling), it is preferable to refine the structure by removing the water-soluble inorganic salt and the water-soluble organic solvent. When a finer pigment is used, the spectral transmittance of the filter segment is improved and the contrast is further increased. At the time of salt milling, a pigment derivative described later, a resin that is at least partially soluble in a water-soluble organic solvent, etc. can be used in combination, and by using a finely-treated pigment obtained by such treatment, more excellent optical properties can be obtained. Filter segments can be formed.

The yellow coloring composition used for formation of the yellow filter segment which the color filter of this invention comprises is demonstrated.
The yellow coloring composition used for the formation of the yellow filter segment includes (a) C.I. I. Pigment Yellow 139, 150, 185, at least one yellow pigment selected from the group consisting of Pigment Yellow 139, 150, 185, (b) a pigment dispersant, and (c) a pigment carrier comprising a transparent resin, a precursor thereof, or a mixture thereof. Including.
The pigment contained in the yellow coloring composition may occupy 5 to 50% by weight of the total weight of the solid content (components other than the solvent) of the yellow coloring composition from the viewpoint of coloring power and stability of the yellow coloring composition. preferable.

  From the viewpoint of dispersibility of the pigment, chromaticity when a pseudo white LED formed by applying a phosphor on the surface of the blue LED is used as a light source, and light resistance, the yellow pigment is C.I. I. It is preferable to use at least one yellow pigment selected from the group consisting of Pigment Yellow 139, 150, and 185. Other usable yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 147, 151, 152, 153, 154, 155, 156 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 187, 188, 193, 194, 199, 198, 213, 214.

  For yellow pigments, a mixture containing a yellow pigment, a water-soluble inorganic salt and a water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt is subjected to salt milling, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed. It is preferable to make it finer. When the refined yellow pigment is used, the spectral transmittance of the yellow filter segment is improved. At the time of salt milling, a basic group-containing derivative, a resin that is at least partially dissolved in a water-soluble organic solvent, a dispersant, or the like can be used in combination. By using the refined yellow pigment obtained by such treatment, a yellow filter segment having more excellent optical properties can be formed.

  In the cyan or yellow coloring composition of the present invention, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow are used in order to ensure good coatability, sensitivity, developability and the like while balancing saturation and lightness. Inorganic pigments such as lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black can be included. . In the cyan coloring composition of the present invention, when these inorganic pigments are used in combination, the inorganic pigment preferably accounts for 0.1 to 10% by weight of the total weight of the pigment. Moreover, in the yellow coloring composition of the present invention, when a pigment other than yellow is used in combination, the yellow pigment accounts for 3 to 70% by weight of the total weight of the pigment from the viewpoint of the lightness of the yellow coloring composition. It is preferable.

  The pigment carrier contained in the cyan coloring composition or yellow coloring composition of the present invention is for dispersing the pigment, and is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Transparent resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that are cured by irradiation with active energy rays to form transparent resins. These can be used alone or in admixture of two or more. The pigment carrier can be used in an amount of preferably 50 to 700 parts by weight, more preferably 100 to 400 parts by weight with respect to 100 parts by weight of the total pigment.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Active energy ray-curable resins include (meth) acrylic compounds having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups. Or a resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting with cinnamic acid. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  The pigment carrier preferably contains a resin obtained by copolymerizing the compound (a) represented by the general formula (1) and another compound (b) having an ethylenically unsaturated double bond. Since the transparent copolymer resin exhibits an excellent dispersion effect for almost all pigments, it functions to prevent aggregation of the pigments in the coloring composition and to maintain a finely dispersed state of the pigments. Therefore, when the filter segment is formed by using the cyan colored composition or the yellow colored composition of the present invention obtained by dispersing the pigment in the pigment carrier containing the transparent copolymer resin, the filter segment having less pigment aggregates. A color filter with high transmittance and high brightness can be manufactured.

式（１）において、Ｒ₁₄は、水素原子またはメチル基を表す。Ｒ₁₅はアルキレン基を表す。Ｒ₁₆は、水素原子またはベンゼン環などの置換基を含んでも良い炭素数１〜２０のアルキル基を表す。ｍは１〜１５の整数を表す。

In the formula (1), R ₁₄ represents a hydrogen atom or a methyl group. R ₁₅ represents an alkylene group. R ₁₆ represents a C 1-20 alkyl group which may contain a substituent such as a hydrogen atom or a benzene ring. m represents an integer of 1 to 15.

The compound (a) represented by the general formula (1) which is a constituent component of the transparent copolymer resin has good adsorption / orientation on the pigment surface due to the effect of π electrons of the benzene ring. In particular, when (a) is paracumylphenol ethylene oxide or propylene oxide modified (meth) acrylate, its steric effect is added and a better adsorption / orientation plane can be formed on the pigment, which is more effective. . The alkyl group represented by R ₁₆ has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. When the carbon number of the alkyl group represented by R ₁₆ is 1 to 10, the alkyl group becomes an obstacle and suppresses the approach between the resins and promotes adsorption / orientation to the pigment, but when the carbon number exceeds 10, The steric hindrance effect of the alkyl group is increased, preventing the adsorption / orientation of the benzene ring to the pigment surface. This becomes more prominent as the chain length of the alkyl group represented by R ₁₆ becomes longer, and when the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely lowered.

Examples of the compound (a) include phenol ethylene oxide modified (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate and the like.
As the compound (b), (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso) butyl (meth) acrylate, (iso) pentyl (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate acid phosphooxyethyl (meth) Examples thereof include acrylate, acid phosphooxypropyl (meth) acrylate, 3 chloro 2-acid phosphooxyethyl (meth) acrylate, and acid phosphooxypolyethylene glycol mono (meth) acrylate.

The proportion of the compound (a) in the transparent copolymer resin is preferably 0.1 to 50% by weight, more preferably 10 to 35% by weight. When the proportion of the compound (a) is less than 0.1% by weight, a sufficient pigment dispersion effect cannot be obtained, and when it is more than 50% by weight, the compatibility with other components in the coloring composition is lowered. In some cases, precipitation of the monomer or photopolymerization initiator may occur.
The weight average molecular weight (Mw) of the transparent resin is preferably 5,000 to 100,000, more preferably 10,000 to 50,000.

  As monomers and oligomers that are pigment carriers, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (Meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate , Neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) Various acrylates and methacrylates such as acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl ( Examples include meth) acrylamide, N-vinylformamide, acrylonitrile, and the like, and these can be used alone or in combination of two or more.

The cyan or yellow coloring composition for a color filter of the present invention is a three-roll mill, a two-roll mill, a sand mill, a kneader, an attritor, etc. These can be produced by finely dispersing using various dispersing means. When two or more kinds of pigments are used, the respective pigments can be mixed in advance, and the resulting pigment mixture can be finely dispersed in a pigment carrier.
When the pigment is dispersed in the pigment carrier, a dispersion aid such as a pigment derivative, a resin-type pigment dispersant, or a surfactant can be appropriately used. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, when a coloring composition obtained by dispersing the pigment in the pigment carrier using the dispersion aid is used. Provides a color filter excellent in transparency. The dispersion aid can be used in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the total pigment.

The pigment derivative is a compound represented by the following general formula (2), and there are those having a basic substituent and those having an acidic substituent.
AB General formula (2)
In formula (2), A represents an organic pigment residue, and B represents a basic substituent or an acidic substituent.

  In the formula (2), the organic pigment constituting the organic pigment residue represented by A includes diketopyrrolopyrrole pigments, azo pigments such as azo, disazo and polyazo, copper phthalocyanine, copper halide phthalocyanine, none Phthalocyanine pigments such as metal phthalocyanines, aminoanthraquinones, diaminodianthraquinones, anthrapyrimidines, anthraquinone pigments such as flavantrons, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigments, dioxazine pigments, perinone pigments, perylenes Examples thereof include pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  In the formula (2), examples of the basic substituent represented by B include substituents represented by the following formula (3), formula (4), formula (5), and formula (6). Examples of the acidic substituent represented include substituents represented by the following formula (7), formula (8), and formula (9).

In formulas (3) to (6),
X represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10.
R ₁ and R ₂ are each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, Alternatively, R ₁ and R ₂ together represent a heterocyclic ring which may further contain a nitrogen, oxygen or sulfur atom and may be substituted.

R ₃ represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or Represents an optionally substituted phenyl group.
Y represents —NR ₈ —Z—NR ₉ — or a direct bond. Here, R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or a substituted group. Represents a good phenyl group.

Z represents an alkylene group having 1 to 36 carbon atoms which may be substituted, an alkenylene group having 2 to 36 carbon atoms which may be substituted, or a phenylene group which may be substituted.
R represents a substituent represented by the following formula (10) or a substituent represented by the following formula (11).
Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the following formula (10) or a substituent represented by the following formula (11).

式（１０）および式（１１）において、Ｒ₁〜Ｒ₇およびｎは、上に定義した通りのものである。

In Formula (10) and Formula (11), R _{1 to} R ₇ and n are as defined above.

Formula (7): -SO ₃ M
Formula (8): -COOM

In formulas (7) and (8), M represents 1 / i hydrogen atom, calcium atom, barium atom, strontium atom, manganese atom or aluminum atom, and i represents the valence of M. For example, in the formula (7), M represents one hydrogen atom, one-half calcium atom (in this case, two COO- bonds to one atom of calcium) and the like.
In the formula (9), R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, or a substituted group having 2 to 36 carbon atoms. An alkenyl group that may be substituted, a phenyl group that may be substituted, or a polyoxyalkylene group.

  Examples of the amine component used to form the substituents represented by formula (3) to formula (6), formula (10), and formula (11) include dimethylamine, diethylamine, N, N-ethylisopropyl, and the like. Amine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine N, N-methyloctadecylamine, didecyl Min, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N -Diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N Methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidineethanol, Pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl- 4-Pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like can be mentioned.

  The amine component used to form the sulfonic acid amine salt of formula (9) may be any of primary, secondary, tertiary and quaternary amines. For example, primary amines have side chains. Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, An amine such as eocosylamine, or an unsaturated amine corresponding to each carbon number can be mentioned.

Secondary, tertiary and quaternary amines include dioleylamine, distearylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylstearylamine, dilaurylmonomethylamine, trioctylamine, dimethyldidodecylammonium chloride, Dimethyl dioleyl ammonium chloride, dimethyl didecyl ammonium chloride, dimethyl dioctyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl decyl ammonium chloride, trimethyl hexadecyl ammonium chloride, trimethyl octadecyl ammonium chloride, dimethyl dodecyl tetradecyl ammonium chloride , Dimethyl hexadecyl octadec Ammonium chloride, and the like.
Further, when any of R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ in the formula (9) represents a polyoxyalkylene group, examples thereof include a polyoxyethylene group and a polyoxypropylene group.

  The resin-type pigment dispersant has a pigment affinity part having a property of adsorbing to the pigment and a part compatible with the pigment carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the pigment carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Oil-based dispersants such as salts; water-soluble such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based or the like is used. These can be used alone or in admixture of two or more.

  Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, dodecyl sulfate. Anions such as monoethanolamine, triethanolamine dodecyl sulfate, ammonium dodecyl sulfate, monoethanolamine stearate, sodium stearate, sodium dodecyl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Surfactants: polyoxyethylene oleyl ether, polyoxyethylene dodecyl ether, polyoxyethylene nonyl pheny Nonionic surfactants such as ethers, polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts Agent: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, which can be used alone or in admixture of two or more.

When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the yellow coloring composition or the cyan coloring composition.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenone photopolymerization initiators such as -1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p -Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (Trichloromethyl) -s-triazine, 2,4-bis (trick (Romethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used. A photoinitiator can be used in the quantity of 5-150 weight part with respect to a total of 100 weight part of a pigment.

  The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenance are used. Such as lenquinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. A compound can also be used in combination. The sensitizer can be used in an amount of 0.1 to 150 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

  In the colored composition of the present invention, a pigment is sufficiently dispersed in a pigment carrier, and is applied on a substrate such as a glass substrate so as to have a dry film thickness of 0.5 to 5 μm to form a filter segment. A solvent can be included for ease. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether acetate, propylene Examples include glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, and petroleum solvents, and these are used alone or in combination. A solvent can be used in the quantity of 500-4000 weight part with respect to a total of 100 weight part of a pigment.

In addition, the colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the pigment.
The coloring composition for a color filter of the present invention can be prepared in the form of a solvent developing type or alkali developing type coloring resist material, gravure offset printing ink, silk screen printing ink, ink jet printing ink and the like. The colored resist material is obtained by dispersing a predetermined pigment in a composition containing the thermoplastic resin, thermosetting resin or active energy ray curable resin, the monomer, and the photopolymerization initiator.

The yellow pigment, or the phthalocyanine blue pigment and the phthalocyanine green pigment are 1.5 to 12 in total in the yellow coloring composition or the cyan coloring composition containing a solvent when the filter segment is formed by a photolithography method. It is preferable to contain it in the ratio of weight%. Further, the yellow pigment, the phthalocyanine blue pigment and the phthalocyanine green pigment are preferably contained in the final filter segment in a proportion of preferably 10 to 60% by weight, more preferably 20 to 50% by weight, It consists essentially of a resinous binder provided by a pigment carrier.
The colored composition of the present invention can be obtained by means of centrifugal separation, sintered filter, membrane filter, or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

Next, the color filter of the present invention will be described.
The color filter of the present invention includes a red filter segment, a green filter segment, a blue filter segment, and a yellow filter segment. I. A yellow coloring composition comprising at least one yellow pigment selected from the group consisting of Pigment Yellow 139, 150 and 185, a pigment dispersant, and a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof. It is formed using.
The color filter of the present invention can be produced by forming each color filter segment using a colored composition on a transparent or light reflective substrate by a printing method or a photolithography method.

  The red filter segment can be formed using a normal red coloring composition. The red coloring composition is, for example, C.I. instead of the phthalocyanine blue pigment and phthalocyanine green pigment in the cyan coloring composition of the present invention. I. Pigment Red 7, 14, 41, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279 and the like. The red coloring composition includes C.I. I. An orange pigment such as Pigment Orange 43, 71, 73 can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition. The blue coloring composition is, for example, C.I. instead of the phthalocyanine blue pigment and phthalocyanine green pigment in the cyan coloring composition of the present invention. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and the like. Blue coloring compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

  The magenta color filter segment can be formed using an ordinary magenta color coloring composition. The magenta colored composition is, for example, C.I. instead of the phthalocyanine blue pigment and phthalocyanine green pigment in the cyan colored composition of the present invention. I. Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 192, 202, 207, 209, C.I. I. It is a composition obtained by using a pigment such as Pigment Violet 19.

As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is coated with silica, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.
As the light-reflective substrate, silicon or a substrate obtained by forming an aluminum, silver, silver / copper / palladium alloy thin film on the transparent substrate is used.

  The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When each color filter segment is formed by photolithography, the colored composition prepared as the solvent developing type or alkali developing type colored resist material is applied on the substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it apply | coats so that a dry film thickness may be set to 0.5-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. .
The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired substrate.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the light reflective substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the light reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

Finally, the liquid crystal display device of the present invention will be described.
The liquid crystal display device of the present invention comprises the color filter of the present invention and a pseudo white LED light source (backlight light source or front light light source). The pseudo white LED is a blue LED having a fluorescent filter formed on the surface thereof, or a blue LED resin package containing a phosphor, and has a wavelength λ1 at which the emission intensity becomes maximum within a wavelength range of 430 nm to 485 nm. The emission intensity peak wavelength λ2 within the wavelength range of 530 nm to 580 nm, and the ratio I2 / I1 of the emission intensity I2 at the wavelength λ2 to the emission intensity I1 at the wavelength λ1 is 0.2 or more and 0.7 or less Spectral characteristics are The blue LED is an LED that emits blue light (wavelength is, for example, 470 nm) such as InGaN or GaN. The fluorescent filter absorbs part of the blue light emitted from the blue LED and emits yellow light having a maximum light emission between 500 and 600 nm. In this type of white LED, part of the blue light emitted by the blue LED passes through the phosphor layer, and the rest is absorbed by the phosphor and converted into yellow light. The observer recognizes light in which two colors of blue light and yellow light are mixed as white light. Examples of the phosphor that converts blue light into yellow light include YAG (yttrium, aluminum, garnet). Such a pseudo white LED is available from NSPA 300BS, NSPW310BS, NSPW312BS, NSPW315BS, NSPW500BS, NEPW500, etc. manufactured by Nichia Corporation. By using a pseudo white LED light source having such spectral characteristics in combination with the color filter of the present invention, the color reproduction region of the liquid crystal display device can be further expanded.

  The liquid crystal display device of the present invention is a liquid crystal display device comprising the color filter of the present invention and a cold cathode fluorescent tube light source (backlight light source or front light light source). The cold cathode fluorescent tube light source has a wavelength λ3 at which the emission intensity is maximized within a wavelength range of 470 nm to 530 nm, and has a wavelength λ4 at which the emission intensity is maximized within a wavelength range of 530 nm to 580 nm. It has a spectral characteristic in which the ratio (I3 / I4) of the emission intensity I3 at the wavelength λ3 to the emission intensity I4 is 0.2 or more and 0.7 or less. By using a cold cathode fluorescent tube light source having such spectral characteristics in combination with the color filter of the present invention, the color reproduction region of the liquid crystal display device can be further expanded. Such a cold cathode fluorescent tube can be reproduced by F10 or the like.

The liquid crystal display device of the present invention is a liquid crystal display device comprising the color filter of the present invention and three color (red, green and blue) LED light sources (backlight light source or front light light source). The three-color LED light source is one in which a fluorescent filter is formed on the surface of a blue LED or a blue LED resin package containing a phosphor, and the emission intensity is maximized within a wavelength range of 430 nm to 485 nm. It has a wavelength λ5, a wavelength λ6 where the emission intensity is maximized within the wavelength range of 530 nm to 580 nm, and the ratio I6 / I5 of the emission intensity I6 at the wavelength λ6 to the emission intensity I5 at the wavelength λ5 is 0.2 or more Spectral characteristics of 0.7 or less. The blue LED is an LED that emits blue light (wavelength is, for example, 470 nm) such as InGaN or GaN. The fluorescent filter absorbs part of the blue light emitted from the blue LED and emits green light having a maximum light emission between 530 nm and 580 nm and red light having a maximum light emission between 610 nm and 670 nm. In this type of three-color LED, part of the blue light emitted by the blue LED passes through the phosphor layer, and the rest is absorbed by the phosphor and converted into green and red light. Examples of the phosphor that converts blue light into green light include CaGa ₂ S ₄ : Eu crystals, and examples of the phosphor that converts blue light into green light include CaS: Eu crystals. An observer recognizes light in which three colors of light of blue light emission, green light emission, and red light emission are mixed as white light. Such a three-color LED is available from SDPW50B0B, SDPW50H0B, SDPW3DG0B, etc. manufactured by Seiwa Electric Co., Ltd. By using a three-color LED light source having such spectral characteristics in combination with the color filter of the present invention, the color reproduction region of the liquid crystal display device can be further expanded.

The color characteristics of a liquid crystal display device having a color filter and a light source are determined by the transmission spectrum of the color filter and the light characteristics of the light source, and are determined by the wavelength distribution of the product of the spectral intensity distribution of the light source and the transmission spectrum of the color filter. . In order to expand the color reproduction region when the panel is formed, it is preferable that the cyan transmission spectrum and the spectral intensity distribution of the light source have a large overlap and the emission intensity is higher. Therefore, a cold cathode fluorescent tube light source and a three-color LED light source having the above spectral characteristics are preferable.
On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.

The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.
Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter.

  FIG. 1 is a schematic cross-sectional view of a color liquid crystal display device 10 having a backlight unit to which the color filter of the present invention can be applied. A color liquid crystal display device 10 shown in FIG. 1 is a typical example of a TFT drive type liquid crystal display device for a notebook personal computer, and includes a pair of transparent substrates 11 and 21 disposed so as to be opposed to each other. Is filled with a liquid crystal composition (for example, TN or STN liquid crystal composition) LC. A TFT array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. Filter segments such as red, green, blue, cyan, yellow, magenta and the like constituting the color filter are separated by a black matrix (not shown). A transparent electrode layer 23 made of, for example, ITO is formed so as to cover the color filter 22, and an alignment layer 24 is provided so as to cover the transparent electrode layer 23. A polarizing plate 25 is formed on the outer surface of the transparent substrate 21.
A backlight unit 30 including a light source (pseudo white LED light source, cold cathode fluorescent tube light source or three-color LED light source) 31 is provided in close contact with the polarizing plate 15 outside the first transparent substrate 11.

FIG. 2 is a perspective view of the backlight unit 30 of FIG. The backlight unit 30 includes a light source 31, a light guide plate 33, and a diffusion plate 34 provided on the upper surface of the light guide plate 33. The light source 31 is provided so as to face one side surface 33 a of the light guide plate 33, and is surrounded by the reflector 32 over the entire length except for a portion corresponding to the side surface 33 a of the light guide plate 33. The light guide plate 33 is covered with the reflection plate 35 on the other three side surfaces and the bottom surface except the side surface 33a. Light from the light source 31 is guided to the light guide plate 33 by the reflector 32, passes through the diffusion plate 34, becomes planar light, and enters the liquid crystal layer LC from the polarizing plate 15. The reflection plate 35 efficiently directs the light incident on the light guide plate 33 toward the diffusion plate 34.
With reference to FIG. 1, a liquid crystal display device having a pseudo white LED light source, a cold cathode fluorescent tube light source, or a three-color LED light source as a backlight light source has been described. Needless to say, the present invention includes a pseudo white LED light source, The present invention can also be applied to a liquid crystal display device having a cold cathode fluorescent tube light source or a three-color LED light source as a front light source.

Hereinafter, the present invention will be described by way of examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
(Preparation of acrylic resin solution 1)
Place 800 parts of cyclohexanone in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 100 ° C. while injecting nitrogen gas into the vessel. A mixture of 60.0 parts of styrene, 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate, 65.0 parts of butyl methacrylate, and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to polymerize the reaction. Went.
After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain a weight average molecular weight. Of about 40000 (measured by GPC).
After cooling to room temperature, about 2 g of the resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Based on the measured value, the previously synthesized resin solution has a nonvolatile content of 20%. Thus, cyclohexanone was added to prepare an acrylic resin solution 1.

(Preparation of acrylic resin solution 2)
In a reaction vessel similar to the preparation of the acrylic resin solution 1, 700 parts of cyclohexanone was charged, the temperature was raised to 80 ° C., and the inside of the reaction vessel was purged with nitrogen, and then 133 parts of n-butyl methacrylate and 46 of 2-hydroxyethyl methacrylate were added from the dropping tube. Part mixture, 43 parts methacrylic acid, 74 parts paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 4.0 parts 2,2′-azobisisobutyronitrile over 2 hours The polymerization reaction was performed dropwise.
After the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution having a weight average molecular weight of about 26000 (measured by GPC).
After cooling to room temperature, about 2 g of the resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Based on the measured value, the previously synthesized resin solution has a nonvolatile content of 20%. Thus, cyclohexanone was added to prepare an acrylic resin solution 2.

(Preparation of yellow treated pigment 1)
500 parts of isoindolinone-based yellow pigment (CI Pigment Yellow 139, “Irgafoa Yellow 2R-CF” manufactured by Ciba Specialty Chemicals), 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a 1 gallon kneader made of stainless steel (Inoue And kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow-treated pigment 1 were obtained.

(Preparation of yellow treated pigment 2)
500 parts of isoindolinone-based yellow pigment (CI Pigment Yellow 139, “Irgafoa Yellow 2R-CF” manufactured by Ciba Specialty Chemicals), 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a 1 gallon kneader made of stainless steel (Inoue And kneaded at 120 ° C. for 2 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow-treated pigment 2 were obtained.

(Preparation of yellow-treated pigment 3)
500 parts of isoindoline-based yellow pigment (CI Pigment Yellow 185, "Pariol Yellow D1155" manufactured by BASF), 500 parts of sodium chloride, and 250 parts of diethylene glycol are charged into a 1 gallon kneader (manufactured by Inoue Seisakusho), 120 The mixture was kneaded at 0 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow-treated pigment 3 were obtained.

(Preparation of yellow-treated pigment 4)
500 parts of isoindoline-based yellow pigment (CI Pigment Yellow 185, "Pariol Yellow D1155" manufactured by BASF), 500 parts of sodium chloride, and 250 parts of diethylene glycol are charged into a 1 gallon kneader (manufactured by Inoue Seisakusho), 120 The mixture was kneaded at 2 ° C. for 2 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow-treated pigment 4 were obtained.

(Preparation of yellow-treated pigment 5)
500 parts of a metal complex yellow pigment (CI Pigment Yellow 150, “E-4GN” manufactured by LANXESS), 500 parts of sodium chloride, and 250 parts of diethylene glycol are charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), 120 The mixture was kneaded at 0 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow-treated pigment 5 were obtained.

(Preparation of yellow-treated pigment 6)
Quinophthalone yellow pigment (CI Pigment Yellow 138, BASF
500 parts of “Paliotol Yellow K0960-HD”, 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 2 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow-treated pigment 6 were obtained.

(Preparation of yellow treated pigment 7)
Anthraquinone yellow pigment (CI Pigment Yellow 199, Ciba
500 parts of “Chromophthal Yellow GT-A0” manufactured by Specialty Chemicals Co., Ltd., 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 2 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow-treated pigment 7 were obtained.

(Preparation of blue-treated pigment 1)
200 parts of phthalocyanine blue pigment (CI Pigment Blue 15: 3, “Lionol Blue FG-7351” manufactured by Toyo Ink Co., Ltd.), 1500 parts of sodium chloride, and 1500 parts of diethylene glycol were added to a 1 gallon kneader (Inoue). And kneaded at 100 ° C. for 7 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. Thus, a blue-treated pigment 1 was obtained.

(Preparation of green treated pigment 1)
200 parts of phthalocyanine-based green pigment (CI Pigment Green 7, “Lionol Green Y-101” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1200 parts of sodium chloride, and 1200 parts of diethylene glycol are made of 1 gallon kneader (manufactured by Inoue Seisakusho). And kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green-treated pigment 1 was obtained.

(Preparation of pigment dispersion)
After stirring and mixing uniformly 130 parts of the pigment, pigment derivative 1-9 and acrylic resin solution mixture shown in Table 1 and 120 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), zirconia beads having a diameter of 1.0 mm Then, the mixture was dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours and then filtered with a 5 μm filter to prepare a pigment dispersion.
Below, the structure of the pigment derivatives 1-9 is shown.

* 1 Phthalocyanine blue pigment manufactured by Toyo Ink Co., Ltd. (CI Pigment Blue 15: 6)
* 2 Anthraquinone red pigment (CI Pigment Red 177) manufactured by Ciba Specialty Chemicals
* 3 Isoindolinone yellow pigment manufactured by BASF (CI Pigment Yellow 139)
* 4 Phthalocyanine green pigment (CI Pigment Green 36) manufactured by Toyo Ink Co., Ltd.
* 5 LANXESS metal complex yellow pigment (CI Pigment Yellow 150)
* 6 Clariant's dioxazine purple pigment (CI Pigment Violet 23)
* 7 Clariant dye lake pigment (CI Pigment Red 81: 2)

(Preparation of colored composition 1)
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain an alkali developing type cyan coloring composition 1.

Pigment Dispersion 2 shown in Table 1 12.0 parts Pigment Dispersion 3 shown in Table 1 48.0 parts Photopolymerization initiator 2.0 parts ("Irgacure 907" manufactured by Ciba Specialty Chemicals)
5.0 parts of trimethylolpropane triacrylate (“NK ESTER ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.5 parts acrylic resin solution 1 2.5 parts cyclohexanone 30.0 parts

(Coloring composition 2-18)
Except having used the pigment dispersion shown in Table 2, it carried out similarly to the coloring composition 1, and obtained the coloring compositions 2-18.

(Preparation of colored composition coated substrate)
The obtained colored composition was spin-coated on a 100 mm × 100 mm substrate having a thickness of 0.7 mm so that the average film thickness was 4 μm, and dried at 70 ° C. for 20 minutes. Then, UV exposure was performed with an integrated light amount of 300 mJ / cm ² . The coated substrate of each colored composition was obtained by heating the coated substrate at 230 ° C. for 40 minutes.
(Measurement of hue (x, y, Y) of colored composition coated substrate)
The hue of the obtained coated substrate was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 2.

(Evaluation of contrast ratio)
About the coloring composition application | coating board | substrate, the contrast was measured by the following method using the measuring apparatus shown in FIG.
A glass substrate 5 provided with a colored composition dry coating film 4 is sandwiched between two polarizing plates 3 and 6, and light is irradiated from one polarizing plate 6 side using a backlight unit 7 for a liquid crystal display device. . The light emitted from the backlight unit passes through the first polarizing plate 6 and is polarized, and then passes through the colored composition dry coating film 4 and the glass substrate 5 to reach the second polarizing plate 3. If the polarization axes of the first polarizing plate 6 and the second polarizing plate 3 are parallel to each other, light is transmitted through the second polarizing plate 3, but the polarization axes of both polarizing plates are perpendicular to each other. If it is, the light is blocked by the second polarizing plate 3. However, when the light polarized by the first polarizing plate 6 passes through the colored composition-coated substrate, if the light is scattered by pigment particles and a part of the polarization plane is shifted, the polarization of both polarizing plates When the axes are parallel, the amount of light transmitted through the second polarizing plate 3 is reduced, and when the polarization axes of both deflecting plates are orthogonal, a part of the light is transmitted through the second polarizing plate 3. The luminance of this transmitted light is measured with the luminance meter 1 on the polarizing plate 3, and the luminance when the polarization axes of both polarizing plates are parallel to the luminance when the polarization axes of both polarizing plates are orthogonal (brightness when orthogonal). Let the ratio of (parallel brightness) be the contrast ratio. That is, the contrast ratio is calculated by the following equation.

Contrast ratio = (Parallel luminance) / (Orthogonal luminance)
Accordingly, when scattering occurs due to the pigment in the colored composition coating film, the parallel brightness decreases and the orthogonal brightness increases, and the contrast ratio decreases.
The luminance meter used was “Color Luminance Meter BM-5A” manufactured by Topcon Corporation, and the polarizing plate used was “Polarized Film LLC2-92-18” manufactured by Sanritsu. In the measurement, a black mask 2 having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.
(Evaluation of light resistance)
The colored composition-coated substrate was exposed to light with a light resistance evaluation apparatus (“Suntest CPS +” manufactured by Toyo Seiki Co., Ltd.) for 500 hours, and the color difference ΔE before and after the light resistance evaluation was measured.

[Examples 1 to 14 and Comparative Examples 1 to 6]
(Production of color filter)
A black matrix was patterned on a glass substrate, and the colored composition 8 was applied on the substrate with a spin coater to form a coating film of the colored composition. The coating was irradiated with 300 mJ / cm ² of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, the undeveloped portion was removed by spray development with an alkali developer composed of a 2% by weight aqueous sodium carbonate solution, and then washed with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a film thickness of 2.5 μm. Red filter segments were formed. By the same method, a green filter segment and a blue filter segment having a film thickness of 2.5 μm were formed using the colored compositions 9 and 10. By the same method, a color filter was produced by forming cyan, yellow, and magenta filter segments having a film thickness of 2.5 μm using the colored compositions 1 to 18 shown in Table 4.

(Evaluation of color reproduction area)
A pseudo white LED light source (“NSPW300BS” manufactured by Nichia Chemical Co., Ltd.) using the color filter produced using the above colored composition (wavelength λ1 at which the emission intensity is maximized within the wavelength range of 430 nm to 485 nm in Table 3) , Emission intensity I1, wavelength λ2 and emission intensity I2 having the maximum emission intensity in the wavelength range of 530 nm to 580 nm, and cold cathode fluorescent tube light source (F10 light source) (Table 3 shows the wavelength range of 470 nm to 530 nm). The wavelength λ3, the emission intensity I3, the wavelength λ4, and the emission intensity I4, the maximum emission intensity within the wavelength range of 530 nm to 580 nm, are shown.) Three-color LED light source (manufactured by Seiwa Electric Co., Ltd.) “SDPW50B0B”) (Table 3 shows the wavelength λ5 and the emission intensity I5 that are the maximum of the emission intensity within the wavelength range of 430 nm to 485 nm. NTSC ratio of the color filter when the light is irradiated using the wavelength λ6 and the light emission intensity I6 that are the maximum of the light emission intensity in the wavelength range of 530 nm to 580 nm (determined by the US National Television System Committee (NTSC)). The standard system's three primary colors, red (0.67, 0.33), green (0.21, 0.71) and blue (0.14, 0.08), the ratio to the area surrounded by) The ratio of the area of the quadrangle to the area of the reference value was measured with the area of the triangle of three colors of RGB as 100. The evaluation results are shown in Table 4.
In addition, the emission spectrum of the used pseudo white LED light source, cold cathode fluorescent tube, and three-color LED light source is shown in FIG. In FIG. 4, curve a shows the emission spectrum of the pseudo white LED light source, curve b shows the emission spectrum of the cold cathode fluorescent tube, and curve c shows the emission spectrum of the three-color LED light source.

Light source * 1
1: Cold cathode fluorescent tube light source 2: Three-color LED light source 3: Pseudo white LED light source From the results of Table 4, yellow filter segment formed from a yellow coloring composition, Pigment Blue 15: 3 or 15: 4, Pigment Green 7 A color filter including a cyan filter segment formed from a cyan coloring composition containing a high contrast ratio, excellent light resistance, a wide color reproduction region, and excellent performance as a liquid crystal display device.

1 and 2
DESCRIPTION OF SYMBOLS 10 Color liquid crystal display device 11 Transparent substrate 12 TFT array 13, 23 Transparent electrode layer 14, 24 Orientation layer 15, 25 Polarizing plate 21 Transparent substrate 22 Color filter LC Liquid crystal composition 30 Backlight unit 31 Light source 32 Reflector 33 Light guide plate 33a Side surface 34 of light plate 33 Diffuser plate 35 Reflector plate
DESCRIPTION OF SYMBOLS 1 Luminometer 2 Mask 3 Polarizing plate 4 Colored composition dry coating film 5 Glass substrate 6 Polarizing plate 7 Backlight unit

Claims (7)

  A color filter comprising at least a red filter segment, a green filter segment, a blue filter segment, and a yellow filter segment and having an NTCS ratio of 94% to 125%, wherein the yellow filter segment is C.I. I. Pigment Yellow 139, 150, from a yellow coloring composition for a color filter containing at least one yellow pigment selected from the group consisting of Pigment Yellow 139, 150, 185, a transparent resin, and a pigment carrier comprising a precursor thereof or a mixture thereof. A color filter formed.   The pigment in the yellow coloring composition for a color filter is C.I. I. Pigment Yellow 139 and C.I. I. Pigment Yellow 150, and C.I. I. Pigment Yellow 139 / C.I. I. The color filter according to claim 1, wherein the weight ratio of Pigment Yellow 150 is 80/20 to 50/50.   The color filter according to claim 1, further comprising a cyan filter segment.   The color filter according to claim 1, further comprising a magenta color filter segment.   5. A liquid crystal display device comprising: the color filter according to claim 1; and a pseudo white LED light source formed by applying a phosphor on a surface of a blue LED, the pseudo white color The LED light source has a wavelength λ1 at which the emission intensity is maximum within a wavelength range of 430 nm to 485 nm, a peak wavelength λ2 of the emission intensity within a range of wavelengths 530 nm to 580 nm, and the emission intensity I1 at the wavelength λ1. A liquid crystal display device having spectral characteristics in which a ratio I2 / I1 of emission intensity I2 at a wavelength λ2 is 0.2 or more and 0.7 or less.   5. A liquid crystal display device comprising the color filter according to claim 1 and a cold cathode fluorescent tube light source, wherein the cold cathode fluorescent light source emits light within a wavelength range of 470 nm to 530 nm. It has a wavelength λ3 where the intensity is maximum, a wavelength λ4 where the emission intensity is maximum in the wavelength range of 530 nm to 580 nm, and the ratio I3 / I4 of the emission intensity I3 at the wavelength λ3 to the emission intensity I4 at the wavelength λ4 A liquid crystal display device having spectral characteristics of 0.2 to 0.7.   5. A liquid crystal display device comprising the color filter according to claim 1 and a three-color LED light source, wherein the three-color LED light source has a light emission intensity within a wavelength range of 430 nm to 485 nm. It has a wavelength λ5 that is the maximum, a wavelength λ6 that maximizes the emission intensity in the wavelength range of 530 nm to 580 nm, and the ratio I6 / I5 of the emission intensity I6 at the wavelength λ6 to the emission intensity I5 at the wavelength λ5 is 0. A liquid crystal display device having spectral characteristics of 2 or more and 0.7 or less.

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