JP2009217241A - Green colored composition for color filter, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stable green colored composition for color filters, which can form a color filter having high lightness and a high contrast ratio and is excellent in fluidity, various resistance properties and coating properties; and to provide a color filter having high lightness and a high contrast ratio. <P>SOLUTION: The green colored composition for color filters includes: a green pigment component (A) including a pigment carrier comprising a resin, a precursor thereof or a mixture of these and at least a halogenated zinc phthalocyanine pigment; and a mixed organic solvent (B) including an organic solvent (B-1) having a solubility parameter (SP value) of 8.0-10.0 (cal/cm<SP>3</SP>)<SP>1/2</SP>and a boiling point at 760 mmHg of 140-159°C, and an organic solvent (B-2) having a solubility parameter (SP value) of 8.0-10.0 (cal/cm<SP>3</SP>)<SP>1/2</SP>and a boiling point at 760 mmHg of 160-200°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a green coloring composition for a color filter used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter formed using the same.

In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. Increasing demands are being made.
A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.

Until now, in order to realize high brightness and high contrast of the color filter, the pigment contained in the filter segment has been refined. However, various pigments (similarly called crudes having a particle size of 10 to 100 μm produced by chemical reaction, which are made into a mixture of primary particles and aggregated secondary particles by pigmentation treatment) Even if the particles are refined by the refinement treatment method, the pigments whose primary particles or secondary particles have been refined generally tend to agglomerate. When the refinement is too advanced, a huge lump of pigment solid is formed. End up. Furthermore, even if the finely-divided pigment is dispersed in a pigment carrier containing a resin or the like and the secondary particles of the pigment are stabilized as close as possible to the primary particles, a stable coloring composition is obtained. It is very difficult.
A color filter is manufactured by applying and drying a color filter coloring composition (hereinafter also referred to as a coating solution) on a transparent substrate to form a coating film having a thickness of about 0.2 to 5 μm. As the coating method, there are a spin coating method, a die coating method, and the like, which are appropriately used according to the characteristics.

  The spin coating method is widely used for forming a thin film on a relatively small-sized substrate. While rotating the transparent substrate at a constant rotational speed, the coating solution is dropped onto the central portion of the transparent substrate and centrifugal force is applied. Is a coating method in which a coating film having a desired film thickness is formed on the surface of the transparent substrate by extending the coating solution thinly and controlling the number of revolutions and the rotation time of the transparent substrate suitable for the coating solution. However, due to the principle of extending the coating film thinly by utilizing the centrifugal force due to rotation, there is a drawback that the coating film thickness at the rotation center portion and the peripheral portion of the transparent substrate becomes too thick compared to the intermediate portion. In Patent Document 1, a composition containing 50% by weight or more of a solvent having a boiling point or vapor pressure within a specific range is described as a coating solution for a spin coating method having excellent surface smoothness of a coating film.

  When the size of the substrate is large, a method of rotating the substrate such as the spin coating method has a large load on the apparatus, and thus the die coating method is adopted. The die coating method is a coating method in which a coating liquid having a desired film thickness is formed on the surface of a transparent substrate while discharging a coating liquid from a slit and moving the slit. However, due to the mechanism, it is easy for vertical stripes to occur in the direction of the slit, and the coating liquid is exposed to the outside air at the slit opening to dry and solidify, generating aggregates and causing stripe unevenness in the direction of the application. In addition, the agglomerates are mixed into the coated product, resulting in a coating film defect. Furthermore, there is a problem that the outer peripheral portion of the coating film rises and the coating film becomes thicker than the central portion of the substrate.

In order to solve the problem of non-uniformity of the coating film in the die coating method, attempts described in the following patent documents have been made.
Patent Documents 2 and 3 disclose a method in which a coating liquid is prevented from drying and solidifying by containing a high-boiling solvent, and aggregates are not generated.
JP-A-6-3521 JP 2003-55566 A JP 2004-346218 A

On the other hand, as described above, the color filter is required to have not only high contrast but also high brightness. In general, in order to obtain high brightness, when dispersing the pigment in the pigment carrier, the transparency of the dispersion is increased to close to the primary particles, and the spectral spectrum of the dispersion has high transmittance, thereby increasing the brightness. It has gained.
However, green, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate, is a halogenated copper phthalocyanine pigment (for example, CI Pigment Green 36 or CI Pigment) as the main pigment. Although it is common to use green 7), it has been difficult to achieve both high contrast ratio and high brightness as long as copper halide phthalocyanine can be used.

In order to solve these problems, zinc halide phthalocyanine pigments that replace the current copper halide phthalocyanine pigment with zinc as a colorant that exhibits a clear color tone and a wide color display area and has high coloring power. The use of is proposed.
JP-A-10-130547 JP 2001-141922 A JP 2007-204658 A

  However, since the halogenated zinc phthalocyanine pigment is different in chemical properties from the conventional copper halide phthalocyanine pigment and the solubility of the pigment itself is different, the zinc halide phthalocyanine pigment is not suitable for the dispersion of the halogenated copper phthalocyanine pigment. The affinity was too good, and when these solvents were used for the dispersion of zinc phthalocyanine pigment, the pigment itself was dissolved in the solvent, and there was a problem that a dispersion having a high contrast ratio and high brightness could not be obtained. .

  Furthermore, as described above, the coloring composition of the halogenated zinc phthalocyanine pigment dispersed using the solvent used for dispersing the halogenated copper phthalocyanine pigment (Patent Documents 1 to 3) includes a spin coating method and a die coating method. Due to the coating method and the properties of the coating solution used therefor, there were the following drawbacks.

Unevenness of film thickness: Insufficient film thickness uniformity, “film thickness uniformity (edge) = film thickness uniformity of end face” and “film thickness uniformity (other than edge) = substrate It is classified into “uniformity from the center to the front of the end face”.
Stripe: “Striped unevenness that occurs in the direction perpendicular to the slit traveling direction in the horizontal striped die coating method” and “Striped in the slit traveling direction due to the aggregate of slit openings in the vertical striped die coating method” Are classified into two categories.

  An object of the present invention is to reduce a defect observed in a coating film of a coating by a spin coating method and a die coating method, and further to form a color filter having a high brightness and contrast ratio (green resist composition for a color filter). And a color filter comprising a filter segment formed using the same.

The object is for a color filter comprising a pigment carrier comprising a resin, a precursor thereof or a mixture thereof, a green pigment component (A) containing at least a zinc halide phthalocyanine pigment, and an organic solvent (B). A green coloring composition,
The organic solvent (B) has at least a solubility parameter (SP value) of 8.0 to 10.0 (cal / cm ³ ) ^1/2 and a boiling point of 140 to 159 ° C. at 760 mmHg (B— 1) and an organic solvent (B-2) whose solubility parameter (SP value) is 8.0 to 10.0 (cal / cm ³ ) ^1/2 and whose boiling point at 760 mmHg is 160 to 200 ° C. This can be solved by using a green coloring composition for a color filter, which is a mixed organic solvent.

  Here, the organic solvent (B-1) is at least one solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate. preferable.

  The organic solvent (B-2) is preferably one or more solvents selected from cyclohexyl acetate, propylene glycol diacetate, diethylene glycol diethyl ether, and ethyl 3-ethoxypropionate.

In the preferable aspect of the green coloring composition for color filters by this invention, the organic solvent (B-1) is 50 to 95 weight% on the basis of the whole quantity of the organic solvent (B), and the organic solvent (B-2). ) Is 5 to 50% by weight.
In the preferable aspect of the green coloring composition for color filters by this invention, a photoinitiator is further included.

  The present invention also relates to a color filter comprising a green filter segment formed from the green coloring composition for a color filter.

A pigment carrier comprising a resin, its precursor or a mixture thereof, a green pigment component (A) containing at least a zinc halide phthalocyanine pigment, and a solubility parameter (SP value) of 8.0 to 10.0 (cal / cm ^3). ) ^1/2, an organic solvent having a boiling point at 760mmHg is 140~159 ℃ (B-1), solubility parameter (SP value) in 8.0~10.0 (cal / cm ^{3) 1/2} And a mixed organic solvent (B) containing an organic solvent (B-2) having a boiling point of 160 to 200 ° C. at 760 mmHg, and using the green composition for a color filter of the present invention, It is possible to form a color filter having a high contrast ratio and lightness with reduced defects observed in the coating film.

  First, the green coloring composition of the present invention will be described in detail with reference to preferred embodiments. The green coloring composition of this invention contains the pigment carrier which consists of resin, its precursor, or those mixtures, a green pigment component (A), and the organic solvent (B).

[Green pigment component (A)]
The green coloring composition for color filters of the present invention is characterized by using at least a zinc halide phthalocyanine pigment as a main pigment.

  A typical zinc halide phthalocyanine pigment represented by a color index (CI) number is C.I. I. And a green pigment such as CI Pigment Green 58. By using a halogenated zinc phthalocyanine pigment as the main pigment, high brightness not obtained with other green pigments can be obtained. In particular, the amount of acidic functional groups on the pigment surface is 100 μmol / g or more when measured using n-hexylamine as a basic substance by the method described in Colorant, 67 [9], 547-554 (1994), Furthermore, the thing of 200 micromol / g or more is preferable.

  The pigment used in the present invention is not limited to the zinc halide phthalocyanine pigment that is the main pigment, but may be used in combination with other green pigments and yellow pigments for the purpose of color adjustment and complementary color.

  Other green pigments that can be used in combination include C.I. I. Pigment Green 7, 10, 36, 37 and the like. Among these, C.I. I. By using in combination with Pigment Green 7 and / or 36, the chromaticity region can be expanded, which is preferable.

  Examples of yellow pigments that can be used in combination 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, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 And the like can be given 182,185,187,188,193,194,198,199,213,214.

  Among these, C.I. I. It is preferable to use together CI Pigment Yellow 139, 150, etc. in that the chromaticity region can be expanded.

  The preferable concentration of the pigment component (A) in all the non-volatile components of the colored composition according to the present invention is 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of obtaining sufficient color reproducibility. Most preferably, it is 20 to 80% by weight. When the concentration of the pigment component (A) is less than 10% by weight, sufficient color reproducibility cannot be obtained, and when it exceeds 90% by weight, the concentration of the pigment carrier is lowered and the stability of the colored composition is poor. Become.

  Particularly preferable pigment ratios include, for example, 50 to 100% by weight of the halogenated zinc phthalocyanine pigment, 0 to 50% by weight of the halogenated copper phthalocyanine pigment, and 0 of the yellow pigment based on the total weight of the pigment component (A). ~ 50% by weight.

  More preferably, based on the total weight of the pigment component (A), the halogenated zinc phthalocyanine pigment is 50 to 90% by weight, the halogenated copper phthalocyanine pigment is 5 to 45% by weight, and the yellow pigment is 5 to 45% by weight. . The chromaticity region can be expanded by such a composition ratio of the pigment.

  The green coloring composition of the present invention using a halogenated zinc phthalocyanine pigment is coated on a glass substrate or the like so as to have the same chromaticity as the green coloring composition using a halogenated copper phthalocyanine, and the transmittance of the coating film Is higher than the coating film of the colored composition using copper phthalocyanine at around 530 nm from around 450 nm. In particular, the transmittance peak shows a transmittance of about 5 to 10% and a value of about 85 to 90%. For this reason, it is possible to combine C.I. I. Pigment Green 36 and C.I. I. High brightness that cannot be obtained with a colored composition using a copper phthalocyanine pigment such as CI Pigment Green 7 can be obtained.

[Miniaturization of pigments]
The pigment used in the green coloring composition of the present invention can be a salt milled and refined product, and it is preferable to use a refined pigment.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt works as a crushing aid, and it is thought that the pigment is crushed using the high hardness of the inorganic salt during salt milling, thereby generating an active surface and causing crystal growth. Yes. Therefore, the crushing of the pigment and the crystal growth occur simultaneously during the kneading, and the primary particle diameter of the pigment obtained varies depending on the kneading conditions.

  In order to promote crystal growth by heating, the heating temperature is preferably 40 to 150 ° C. When the heating temperature is less than 40 ° C., crystal growth does not occur sufficiently, and the shape of the pigment particles becomes close to amorphous, which is not preferable. On the other hand, when the heating temperature exceeds 150 ° C., crystal growth proceeds excessively and the primary particle diameter of the pigment becomes large, which is not preferable as a colorant for the color filter coloring composition. The kneading time for the salt milling treatment is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milling treatment pigment and the cost required for the salt milling treatment.

  By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution in which the primary particle diameter is very fine and the distribution range is wide.

  It is preferable that the primary particle diameter calculated | required by TEM (transmission electron microscope) of the green pigment used for the green coloring composition of this invention is the range of 20-100 nm. When it becomes smaller than 20 nm, dispersion in an organic solvent becomes difficult. On the other hand, if it exceeds 100 nm, a sufficient contrast ratio cannot be obtained. A particularly preferable range is 25 to 85 nm.

  As the water-soluble inorganic salt used for the salt milling treatment, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt and dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent easily evaporates. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, or the like is used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When performing the salt milling treatment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

[Dye derivative]
In the coloring composition for a color filter of the present invention, a dye derivative can be used for the purpose of improving the dispersibility of the pigment. Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment, anthraquinone, acridone, or triazine.
In the present invention, a pigment derivative is particularly preferable, and the structure thereof is a compound represented by the following general formula (1).

General formula (1):
P-Lm
(However, in general formula (1),
P is an m-valent organic pigment residue, an anthraquinone skeleton, an acridone skeleton, or a triazine skeleton,
L is a compound introduced with a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent,
m is an integer of 1-4. )

  Examples of the pigment derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, or JP-B-5-9469. What is currently used can be used, These can be used individually or in mixture of 2 or more types.

The blending amount of the pigment derivative is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 5 to 25 parts by weight with respect to 100 parts by weight of the pigment component (A). If the pigment derivative is less than 1 part by weight relative to 100 parts by weight of the pigment component (A), the dispersibility may be deteriorated, and if it exceeds 50 parts by weight, the heat resistance and light resistance may be deteriorated.
In the general formula (1), examples of the organic pigment constituting the organic pigment residue of P include the following.

For example,
Diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo;
Phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, or metal-free phthalocyanine;
Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone;
Quinacridone pigments; Dioxazine pigments; Perinone pigments; Perylene pigments; Thioindigo pigments; Isoindoline pigments; Isoindolinone pigments; Quinophthalone pigments; Slen pigments; or metal complex pigments.

  In the green coloring composition for a color filter of the present invention, it is also preferable to use a dye derivative for the purpose of improving the dispersibility of the pigment.

(Pigment carrier)
The pigment carrier in which the pigment contained in the green coloring composition of the present invention is dispersed is composed of a resin, a precursor thereof, or a mixture thereof.

  The pigment carrier used in the green coloring composition of the present invention is preferably a resin having a spectral 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. The resin includes a thermoplastic resin, a thermosetting resin, or an active energy ray curable resin, and a precursor thereof includes a monomer or oligomer that is cured by irradiation with an active energy ray to generate a transparent resin. These can be used alone or in admixture of two or more. The pigment carrier can be used in an amount of 30 to 500% by weight based on the total weight of the pigment component (A). If it is less than 30% by weight, the film formability and various resistances are insufficient, and if it exceeds 500% by weight, the pigment concentration is low and color characteristics cannot be expressed.

  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 an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

  When used in the form of an alkali development type colored resist described later, it is preferable to use an alkali-soluble resin having an acidic group such as a (meth) acrylic acid copolymer resin (alkali-soluble acrylic resin). In order to preferably disperse the halogenated zinc phthalocyanine pigment, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 30,000 to 80,000. . The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

In the present invention, the molecular weight distribution (weight average molecular weight (Mw), number average molecular weight (Mn)) of the resin is measured by GPC under the following conditions.
Equipment: GPC-150C (Waters)
Column: GMH-HT 30 cm 2 series (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% ionol added)
Flow velocity: 1.0ml / min
Sample: 0.4ml injection of 0.15% sample

Measurement is performed under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used in calculating the molecular weight of the sample. Furthermore, it calculates by converting into polyethylene by the conversion formula derived | led-out from the Mark-Houwink viscosity formula.

  As an active energy ray-curable resin, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group has a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group ( A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting with a (meth) acrylic compound or cinnamic acid is used. In addition, 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.

Examples of monomers and oligomers that are resin precursors include:
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, Linear or branched alkyl (meth) acrylates such as isomyristyl (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meta ) Acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (Meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, or polyester Glycol monostearyl ether (meth) acrylate of (poly) alkylene glycol monoalkyl ether (meth) acrylates;
(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) (Meth) acrylates having a carboxyl group such as acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, or ω-carboxypolycaprolactone (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl (meth) Phthalates,
Diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate,
Polytetramethylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono ( (Meth) acrylates having hydroxyl groups such as meth) acrylate or glycerol (meth) acrylate;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol-propylene glycol) di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol- Tetramethylene glycol) di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, or 2-ethyl, 2-butyl-propanediol di ( (Poly) alkylene glycol di (meth) acrylates such as (meth) acrylate,
Dimethylol dicyclopentane di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A Di (meth) acrylate, tetramethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, propylene oxide modified bisphenol F di (meth) acrylate, tetramethylene oxide modified bisphenol F di (meth) Acrylate, zinc diacrylate, ethylene oxide-modified phosphate triacrylate, or glycerol di (meth) acrylate Di (meth) acrylate and the like;
(Meth) acrylates having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate;
Glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate Trifunctional or higher polyfunctional (meth) acrylates such as
Glycerol triglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, polyglycerol polyglycidyl ether- (meth) acrylic acid adduct, 1,6-butanediol diglycidyl ether- (Meth) acrylic acid adduct, alkyl glycidyl ether- (meth) acrylic acid adduct, allyl glycidyl ether- (meth) acrylic acid adduct, phenyl glycidyl ether- (meth) acrylic acid adduct, styrene oxide- (meth) Acrylic acid adduct, bisphenol A diglycidyl ether- (meth) acrylic acid adduct, propylene oxide modified bisphenol A diglycidyl ether- (meth) acrylic acid adduct, bisphenol F diglycidyl ether- (meth) acrylic Acid adduct, epichlorohydrin modified phthalic acid- (meth) acrylic acid adduct, epichlorohydrin modified hexahydrophthalic acid- (meth) acrylic acid adduct, ethylene glycol diglycidyl ether- (meth) acrylic acid adduct, polyethylene glycol diglycidyl Ether- (meth) acrylic acid adduct, propylene glycol diglycidyl ether- (meth) acrylic acid adduct, polypropylene glycol diglycidyl ether- (meth) acrylic acid adduct, phenol novolac type epoxy resin- (meth) acrylic acid addition , Cresol novolac type epoxy resin- (meth) acrylic acid adduct, or other epoxy resin- (meth) acrylic acid adduct, etc., epoxy (meth) acrylates;
(Meth) acryloyl-modified isocyanurate, (meth) acryloyl-modified polyurethane, (meth) acryloyl-modified polyester, (meth) acryloyl-modified melamine, (meth) acryloyl-modified silicone, (meth) acryloyl-modified polybutadiene, or (meth) acryloyl-modified rosin (Meth) acryloyl-modified resin oligomers such as;
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether;
Amides such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, or N-vinylformamide; or
Examples include acrylonitrile. These can be used alone or in admixture of two or more, but are not necessarily limited thereto.

[Organic solvent (B)]
In the green coloring composition of the present invention, a filter segment is formed by sufficiently dispersing a pigment in a pigment carrier and applying it on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to facilitate the process, an organic solvent (B) is contained.

As the organic solvent (B), an organic solvent (B-) having a solubility parameter (SP value) of 8.0 to 10.0 (cal / cm ³ ) ^1/2 and a boiling point of 140 to 159 ° C. at 760 mmHg. 1) and an organic solvent (B-2) having a solubility parameter (SP value) of 8.0 to 10.0 (cal / cm ³ ) ^1/2 and a boiling point of 160 to 200 ° C. at 760 mmHg. Use mixed organic solvent.

  More preferably, it is a mixed organic solvent containing an organic solvent (B-1) having a boiling point of 144 to 157 ° C. at 760 mmHg and an organic solvent (B-2) having a boiling point of 164 to 192 ° C. at 760 mmHg.

Here, the organic solvent (B-1) is preferably one or more solvents selected from propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate. The organic solvent (B-2) is preferably at least one solvent selected from cyclohexyl acetate, propylene glycol diacetate, diethylene glycol diethyl ether, and ethyl 3-ethoxypropionate. In addition, cyclohexyl acetate is also called cyclohexanol acetate.
Since the green coloring composition for color filters of the present invention contains a specific range of solubility parameter (SP value) and organic solvent (B-1) having a boiling point and organic solvent (B-2) at a specific ratio, Contrast ratio and high brightness. Moreover, the coating film which apply | coated this coloring composition has the performance which the film thickness nonuniformity and the uneven stripe were reduced, and the film thickness was uniform and was excellent.

When the solubility parameter (SP value) is smaller than 8.0 (cal / cm ³ ) ^1/2 , the dispersion of the zinc halide phthalocyanine pigment becomes worse and more than 10.0 (cal / cm ³ ) ^1/2. When it is increased, the zinc halide phthalocyanine pigment is dissolved in the organic solvent, resulting in a decrease in brightness and contrast ratio.

  When the boiling point is lower than 140 ° C. as the organic solvent (B-1), film thickness unevenness and unevenness are generated, which is not preferable. Moreover, as an organic solvent (B-2), when a boiling point becomes larger than 200 degreeC, tackiness will remain | survive and it is unpreferable.

  The added amount of the solvent can be used in an amount of 800 to 4,000% by weight based on the total amount of the pigment component (A). In addition, the total amount of the solvent is preferably 50 to 95% by weight of the organic solvent (B-1) and 5 to 50% by weight of the organic solvent (B-2). More preferably, the organic solvent (B-1) is 65 to 95% by weight and the organic solvent (B-2) is 5 to 35% by weight.

  If the ratio of (B-1) is out of the range of 50 to 95%, there arises a problem that uneven film thickness and unevenness occur as a coating solution. Thus, for preferable dispersion of the halogenated zinc phthalocyanine pigment, the blending of the organic solvents (B-1) and (B-2) is important.

  Further, as described above, the organic solvent (B-1) used for dispersing the zinc halide phthalocyanine pigment and the green solvent for coating the color filter composition of the present invention are added to improve problems. Although an organic solvent (B-2) is limited to a specific thing, in order to make it easy to form a coloring composition as a filter segment, the following organic solvent can be added as an auxiliary solvent.

  For example, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1, 3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1 -Butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene , O-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether , Ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diisobutyl ketone, diethylene glycol dimethyl ether, diethylene glycol mono Sopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol Monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol phenyl ether, propylene Lenglycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate , Isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester or the like is used.

  In order to obtain a preferable green coloring composition in the present invention, the total of the organic solvent (B-1) and the organic solvent (B-2) is preferably 70% by weight or more in the total organic solvent. More preferably, the total is 80% by weight. The total is particularly preferably 85% by weight or more. When a large amount of an auxiliary solvent other than the organic solvent (B-1) and the organic solvent (B-2) is added, the stability of the halogenated zinc phthalocyanine pigment dispersion and the application of the coating film coated with the coloring composition are applied. It adversely affects workability and is not preferable.

〔dispersion〕
The green coloring composition of the present invention comprises a three-roll mill comprising a green pigment containing at least a zinc halide phthalocyanine pigment, preferably together with a dye derivative, in a pigment carrier comprising the resin, a precursor thereof or a mixture thereof. It can be manufactured by finely dispersing using various dispersing means such as a two-roll mill, a sand mill, a kneader, and an attritor. The green coloring composition of the present invention can also be produced by mixing several types of pigments separately dispersed on a pigment carrier.

  Furthermore, if necessary, it can be prepared in the form of a solvent development type or alkali development type colored resist by adding a photopolymerization initiator or the like. When preparing in the form of an alkali developing type colored resist, an alkali-soluble material having an acidic group in a part of the pigment carrier is used.

(Photopolymerization initiator)
A photopolymerization initiator or the like is added to the green coloring composition for a color filter of the present invention when the composition is cured by ultraviolet irradiation or a filter segment is formed by a photolithographic method. The blending amount when using the photopolymerization initiator is preferably 5 to 200% by weight based on the total amount of the pigment, and more preferably 10 to 150% by weight from the viewpoint of photocurability and developability. preferable.

As the photopolymerization initiator, for example,
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one An acetophenone photopolymerization initiator;
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal;
Benzophenone photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, or 4-benzoyl-4'-methyldiphenyl sulfide;
A thioxanthone photopolymerization initiator such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, or 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 (trichloro) Methyl) -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, or 2,4-trichloromethyl (4′-methoxystyryl) -6 Triazine photopolymerization initiators such as triazine;
Borate photopolymerization initiator;
A carbazole photoinitiator; or
An imidazole photopolymerization initiator or the like is used.

  The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethyl anthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, or 4,4′-diethylaminobenzophenone Can also be used together.

  The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the photopolymerization initiator contained in the colored composition, and 5 to 50 from the viewpoint of photocurability and developability. More preferably, it is% by weight.

[Dispersion aid]
When dispersing the pigment in the pigment carrier, a dispersion aid such as a resin-type pigment dispersant or a surfactant can be appropriately used. The dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a green coloring composition in which the pigment is dispersed in the pigment carrier using the dispersion aid is used. In this case, a color filter having a high spectral transmittance can be obtained.

  The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and acts to stabilize the dispersion of the pigment on the pigment carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, 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, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, and other water-soluble substances Resin, water-soluble polymer, polyester, modified Li acrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, it can be used alone or in admixture of two or more.

As the surfactant, for example,
Sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate Anionic surfactants such as lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, or polyoxyethylene alkyl ether phosphate;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, or polyethylene glycol monolaurate;
Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; or
Examples include alkylbetaines such as alkyldimethylaminoacetic acid betaines, and amphoteric surfactants such as alkylimidazolines, and these can be used alone or in admixture of two or more.

  In addition, the green coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition.

Examples of storage stabilizers include:
Quaternary ammonium chlorides such as benzyltrimethylammonium chloride or diethylhydroxyamine;
Organic acids such as lactic acid or oxalic acid;
Methyl esters of the organic acids;
catechols such as t-butylpyrocatechol;
Organic phosphines such as triphenylphosphine, tetraethylphosphine, or tetraphenylphosphine; or
Examples thereof include phosphites.

[Removal of coarse particles]
The green coloring composition of the present invention is prepared by means of centrifugal separation, sintering filter, membrane filter, etc., and coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more and coarse particles It is preferable to remove the dust.

Thus, it is preferable that a green coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less. (Measurement of particle size by SEM)
The average dispersed particle size is preferably 0.05 to 0.2 μm for increasing the brightness and contrast ratio, and more preferably 0.06 to 0.15 μm because the brightness and contrast ratio can be further increased. .

[Manufacture of color filters]
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. 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 forming a filter segment by a photolithography method, a coating composition such as spray coating, spin coating, slit coating, roll coating, or the like is applied to the transparent composition on the transparent composition prepared as the solvent developing type or alkali developing type coloring resist. To apply a dry film thickness of 0.2 to 5 μm. 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 alkali developer or spraying the developer by spraying 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, 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, a water-soluble or alkaline water-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, etc. 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 manufacturing 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 filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  Next, the color filter of the present invention will be described. The color filter of the present invention comprises at least one red filter segment, at least one blue filter segment, and at least one green filter segment, and the at least one green filter segment comprises the coloring composition for a color filter of the present invention. Formed using.

  The red filter segment can be formed using a normal red coloring composition. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, Red pigments such as 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279 are used.

  The red coloring composition includes C.I. I. Pigment Orange 43, 71, 73, etc. and / or 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, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 It can be used in combination with the yellow pigments such as 182,185,187,188,193,194,198,199,213,214.

  Moreover, a blue filter segment can be formed using a normal blue coloring composition. Examples of the blue coloring composition include C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60 and 64 are used.

  The blue coloring composition includes C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”.
Prior to the examples, the viscosity characteristics of the resist, the lightness of the coating film, the contrast ratio, the method for measuring the maximum transmittance and the method for evaluating the coatability will be described.

(Measurement method of viscosity characteristics)
The viscosity of the resist was measured at a rotational speed of 20 rpm using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.). Furthermore, the ratio of the viscosity at the number of revolutions of 6 rpm and 60 rpm (referred to as thixo index, the larger the value, the higher the thixotropic property) was obtained, and the thixotropic property was evaluated.

(Brightness measurement method)
A film in which the obtained alkali development type resist material is changed by a spin coater, and the chromaticity y in the CIE color system is around 0.62, 0.6 and 0.58 by changing the rotation speed. It was coated to a thickness to prepare a three-point coated substrate. After coating, it was dried in a hot air oven at 80 ° C. for 30 minutes, and the chromaticity was measured. The brightness at y = 0.6 was determined from the three points of measurement data by the primary correlation method. The chromaticity was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.).

(Contrast ratio measurement method)
The contrast ratio of the coating film was measured using the coated substrate used for the brightness measurement. Hereinafter, a method for measuring contrast will be described with reference to FIG.

  The light emitted from the backlight unit for liquid crystal display (7) passes through the polarizing plate (6), is polarized, and passes through the dried coating film (4) of the colored composition applied on the glass substrate (5). And reaches the polarizing plate (3). If the polarization planes of the polarizing plate (6) and the polarizing plate (3) are parallel, light is transmitted through the polarizing plate (3), but if the polarization plane is perpendicular, the light is transmitted by the polarizing plate (3). Blocked. However, when light polarized by the polarizing plate (6) passes through the dried coating film (4) of the colored composition, scattering by pigment particles or the like occurs, and a part of the polarization plane is displaced. Is parallel, the amount of light transmitted through the polarizing plate (3) is reduced, and when the polarizing plate is orthogonal, a part of the light is transmitted through the polarizing plate (3). This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.

(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)
Accordingly, when scattering occurs due to the pigment of the dried coating film (4) of the coloring composition, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered.
A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter (1), and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. 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.

From the obtained three-point contrast ratio and measurement data of chromaticity y, the contrast ratio at y = 0.6 was determined by the primary correlation method.
(Maximum transmittance measurement method)
The maximum transmittance was measured using the coated substrate used for the brightness measurement. After measuring the chromaticity using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), the maximum transmittance at a chromaticity y of 0.6 in the CIE color system was determined by a primary correlation method.

(Evaluation method of coatability)
Next, evaluation of coatability will be described.
Using a coating apparatus of a die coat method and a spin coat method, coating was performed on a glass substrate having a size of 360 mm × 465 mm so as to have an average film thickness of 2.0 μm, and the obtained coated substrate was treated at 70 ° C. for 20 minutes. Pre-baked to obtain a dry coating film. The evaluation items / contents and how to express the results are described below.

<Spin coating method only>
(Thickness uniformity)
“Thickness uniformity (end portion)”: The film thickness was measured every 5 mm from the central portion of the short side end portion of the coated substrate to 5 cm in the substrate center direction. The maximum film thickness was T ₁ , the minimum film thickness was T ₂ , the average film thickness was T, and the film thickness uniformity (edge) was calculated by the following formula (A).
“Thickness uniformity (other than edge)”: The film thickness was measured every 2 cm from the center of the coated substrate to 26 cm in the diagonal direction. Similarly to the above, film thickness uniformity (other than the end portion) was calculated by the following formula (A).
Film thickness uniformity [%] = ((T ₁ −T ₂ ) / T) × 100 (A)
The film thickness uniformity [%] is preferably as small as possible, and less than 4% is evaluated as ○, 4% or more and less than 10% as Δ, and 10% or more as x.

<Die coat method only>
(Vertical stripes)
“Vertical stripe unevenness”: With respect to the die-coated substrate, “vertical stripe unevenness”, which is a stripe-shaped unevenness in the advancing direction of the slit due to the aggregate of the slit opening, was evaluated with white transmitted light. The case where there was no stripe unevenness by visual observation was marked with ○, and the case where stripe unevenness was observed was marked with ×.
Next, the acrylic resin solutions used in Examples and Comparative Examples, and their average molecular weight and acid value measurement methods will be described.

(Preparation of acrylic resin solution)
Put 800 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAC) in a reaction vessel, heat to 100 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 60.0 parts of styrene and 60.0 parts of methacrylic acid. A mixture of 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 carry out a polymerization reaction.

  After the addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of PGMAC was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain a weight average molecular weight ( An acrylic resin solution having a Mw) of 40,000 was obtained.

  After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMAC was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. To prepare an acrylic resin solution.

(Measurement of average molecular weight)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the acrylic resin are GPC (Tosoh Corp., HLC-8120GPC) equipped with an RI detector using a TSKgel column (Tosoh Corp.) and THF as a developing solvent. Number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene measured using

(Measurement of acid value)
The acid value (mgKOH / g) of the acrylic resin is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K0070.

  Next, a method for measuring the primary particle size of the pigment and a method for preparing the pigment will be described.

(Primary particle size measurement method)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of the primary particles from an electron micrograph of a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Preparation of green pigment 1)
200 parts of a zinc halide phthalocyanine green pigment (CI Pigment Green 58), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of green pigment 1 were obtained. The primary particle diameter determined by TEM (transmission electron microscope) was 50 nm.

(Preparation of green pigment 2)
A green pigment 2 is obtained in the same manner as the preparation of the green pigment 1 except that the halogenated zinc phthalocyanine green pigment (CI Pigment Green 58) is replaced with a halogenated copper phthalocyanine green pigment (CI Pigment Green 36). It was. The primary particle diameter determined by TEM (transmission electron microscope) was 60 nm.

(Preparation of green pigment 3)
A green pigment 3 is obtained in the same manner as the preparation of the green pigment 1 except that the halogenated zinc phthalocyanine green pigment (CI Pigment Green 58) is replaced with a halogenated copper phthalocyanine green pigment (CI Pigment Green 7). It was. The primary particle diameter determined by TEM (transmission electron microscope) was 60 nm.

(Preparation of yellow pigment)
A yellow pigment was obtained in the same manner as the preparation of the green pigment 1 except that the halogenated zinc phthalocyanine green pigment (CI Pigment Green 58) was replaced with a metal complex yellow pigment (CI pigment yellow 150). The primary particle diameter determined by TEM (transmission electron microscope) was 70 nm.
Next, the preparation method of the green coloring composition (green pigment dispersion) for color filters is demonstrated.

(Preparation of green pigment dispersion 1)
A mixture of 11.0 parts of green pigment 1 (CI Pigment Green 58), 40 parts of acrylic resin solution, 48.0 parts of propylene glycol monomethyl ether acetate (PGMAC), and 1.0 part of resin type dispersant (EFKA4300) After stirring and mixing uniformly, using zirconia beads having a diameter of 0.5 mm, the mixture is dispersed for 5 hours in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then filtered through a 5.0 μm filter to give a green pigment. Dispersion 1 was produced.

  Hereinafter, green pigment dispersions 2 to 8 were obtained in the same manner as the preparation of the green pigment dispersion 1 using the materials shown in Table 1. In addition, the pigment dispersion 5 prepared the pigment dispersion using 9 types of green pigments 1 and 2 parts of yellow pigments.

  Next, a method for measuring and preparing a dispersed particle size of the green resist material will be described.

(Dispersed particle size measurement)
The same result may not be obtained even if the same particle size is measured depending on the measurement principle, equipment, sample preparation method, parameter setting, etc., but in the present invention, the dynamic light scattering method (FFT power The spectrum method is used for measurement.
Using Nikkiso Microtrac UPA-EX150 employing dynamic light scattering (FFT power spectrum method), the particle permeability was absorption mode, the particle shape was non-spherical, and D50 was the average diameter. The diluent solvent for measurement was the same as that used for the dispersion, and the sample treated with ultrasonic waves was measured immediately after preparation.

(Measurement of particle size by SEM)
The particle diameter of the pigment by SEM was measured by a method of directly measuring the maximum particle size from an electron micrograph of a scanning electron microscope (SEM). Specifically, 50 pigment particles are photographed, the short axis diameter and the major axis diameter of the primary particle of each pigment are measured, the average is the particle diameter of the pigment particle, and the maximum is the one Expressed with one significant digit after the decimal point.

Example 1 Preparation of Green Resist Material 1 Green pigment dispersion 1: 60.0 parts Acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.): 4 .2 parts-Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals): 1.2 parts-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts-PGMAC : 15.0 parts ・ Cyclohexyl acetate: 8.2 parts

  The above mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain an alkali developing type green resist material 1. In all the solvents, the blending ratio of PGMAC is 89.8%, and the blending ratio of cyclohexyl acetate is 10.2%. Moreover, the particle diameter by SEM of the dispersed green pigment particles was 0.2 μm.

(Example 2) Preparation of green resist material 2-Green pigment dispersion 1: 60.0 parts-Acrylic resin solution: 11.0 parts-Trimethylolpropane triacrylate ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.2 parts-Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals): 1.2 parts-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Cyclohexyl acetate: 23.2 parts

  The above mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain an alkali developing type green resist material 2. In all the solvents, the blending ratio of PGMAC is 71.0%, and the blending ratio of cyclohexyl acetate is 29.0%. Moreover, the particle diameter by SEM of the dispersed green pigment particles was 0.2 μm.

Examples 3 to 11 Preparation of Green Resist Materials 3 to 11 Green resist materials 3 to 11 were obtained in the same manner as in the preparation of the green resist material 1 using the materials shown in Table 2 below. Table 2 also shows the SEM particle size of the measured resist material.

(Comparative Examples 1-10) Preparation of green resist materials 12-21 Green resist materials 12-21 were prepared in the same manner as green resist material 1 using the materials shown in Table 3. In the green resist materials 12 and 19, 23.2 parts of one kind of solvent are added. Table 3 also shows the SEM particle size of the resist material measured.

  Table 4 shows the characteristic values of the organic solvents used in Examples and Comparative Examples.

Explanation of abbreviations in Table 4.
Boiling point: Boiling point [° C./760 mmHg]
SP: Solubility parameter [(cal / cm ³ ) ^1/2 ]

  Next, a color filter was prepared and evaluated using a red resist material and a green resist material. First, the red resist material used for producing the color filter will be described.

(Production of red pigment dispersion)
C. I. Pigment Red 177 8.0 parts, acrylic resin solution 40 parts, propylene glycol monomethyl ether acetate (PGMAC) 48.0 parts, and resin type dispersant (EFKA4300) 1.0 part were uniformly mixed with stirring, and the diameter was 0. Using a 5 mm zirconia bead, the mixture was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then filtered with a 5.0 μm filter to prepare a red pigment dispersion.

(Preparation of red resist material)
60.0 parts of red pigment dispersion, 11.0 parts of acrylic resin solution, 4.2 parts of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), photopolymerization initiator (manufactured by Ciba Japan Co., Ltd.) Irgacure 907 ") 1.2 parts, a sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts, and a mixture of 23.2 parts of PGMAC were stirred and mixed uniformly. Filtration through a filter gave an alkali developing red resist material.

(Production of color filter)
The red resist material was coated on a 10 cm × 10 cm glass substrate with a spin coater to a thickness of about 2 μm, and left in an oven at 70 ° C. for 15 minutes to remove excess solvent and dry.
Next, stripe pattern exposure was performed using an exposure apparatus. The exposure amount was 100 mJ / cm ² . Further, spray development is performed with a developer composed of a 2% aqueous sodium carbonate solution to remove unexposed portions, and then the substrate is washed with ion-exchanged water. The substrate is heated at 230 ° C. for 30 minutes, and a red filter having a line width of about 50 μm A segment was formed. Next, by the same operation, a filter segment was formed using the green resist material of Example 1 next to the red filter segment, and a color filter having two color filter segments was prepared and evaluated (Example 1). .

  In the same manner, color filters having two color filter segments of red and green were prepared and evaluated using green resist materials 2 to 21 (Examples 2 to 11 and Comparative Examples 1 to 10).

  Tables 5 and 6 show the evaluation results of the viscosity, thixo index, dispersed particle diameter and coating film brightness, contrast ratio, maximum transmittance, and coatability of the resist obtained as described above.

A green pigment component (A) containing at least a zinc halide phthalocyanine pigment, such as the colored compositions (green resist materials 1 to 11) of Examples 1 to 11, and a solubility parameter (SP value) of 8.0 to 10. 0 (cal / cm ³ ) ^1/2 , an organic solvent (B-1) having a boiling point of 140 to 159 ° C. at 760 mmHg, and a solubility parameter (SP value) of 8.0 to 10.0 (cal / cm ³ ) A green composition for a color filter comprising ^1/2 and a mixed organic solvent (B) containing an organic solvent (B-2) having a boiling point of 160 to 200 ° C. at 760 mmHg is dispersed particles. The coating film has a small diameter, excellent fluidity and coating property, and achieves high brightness, high transmittance, and high contrast ratio at the same time. On the other hand, the colored compositions of Comparative Examples 1 to 10 (green resist materials 12 to 21) did not provide a coating film that was satisfactory in terms of brightness, contrast ratio, transmittance, and coatability at the same time.

It is a conceptual diagram of the measuring apparatus for measuring a contrast ratio.

Explanation of symbols

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 (6)

A green coloring composition for a color filter, comprising: a pigment carrier comprising a resin, a precursor thereof or a mixture thereof; a green pigment component (A) containing at least a zinc halide phthalocyanine pigment; and an organic solvent (B). In
The organic solvent (B) has at least a solubility parameter (SP value) of 8.0 to 10.0 (cal / cm ³ ) ^1/2 and a boiling point of 140 to 159 ° C. at 760 mmHg (B— 1) and an organic solvent (B-2) whose solubility parameter (SP value) is 8.0 to 10.0 (cal / cm ³ ) ^1/2 and whose boiling point at 760 mmHg is 160 to 200 ° C. A green coloring composition for a color filter, which is a mixed organic solvent.   The organic solvent (B-1) is at least one solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate. Green coloring composition for color filters.   The organic solvent (B-2) is at least one solvent selected from cyclohexyl acetate, propylene glycol diacetate, diethylene glycol diethyl ether, and ethyl 3-ethoxypropionate. Composition.   The organic solvent (B-1) is 50 to 95% by weight and the organic solvent (B-2) is 5 to 50% by weight based on the total amount of the organic solvent (B). A green coloring composition for color filters.   Furthermore, a photopolymerization initiator is contained, The green coloring composition for color filters in any one of Claims 1-4 characterized by the above-mentioned.   A color filter comprising a green filter segment formed from the green coloring composition for a color filter according to claim 1.

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