JP5381286B2 - Blue coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a blue coloring composition for a color filter. Specifically, the present invention relates to a blue coloring composition for a color filter capable of forming a color filter having high brightness and a wide color reproduction region, and a color filter using the same.

  As an image display device using a color filter, for example, (A) a backlight as a light source, a liquid crystal as an optical shutter, and a combination of color filters having color adjustment functions (color conversion function, color separation function, color correction function, etc.) And (B) a display device composed of a light source and a color filter that is repeatedly turned on and off in a short time according to the display and does not use liquid crystal as an optical shutter.

  Due to diversification of display devices, color filters are required to selectively transmit light with high color purity using various light sources. In order to achieve high selectivity and transmittance, a phthalocyanine pigment that is generally excellent in resistance and color tone is often used in a coloring composition conventionally used for forming a blue filter segment. As this phthalocyanine pigment, those having various central metals such as copper, zinc, nickel, cobalt, and aluminum are known. Among them, copper phthalocyanine is widely used because it has the clearest color tone, but other metal phthalocyanines such as metal-free phthalocyanine, zinc phthalocyanine, and cobalt phthalocyanine other than copper phthalocyanine have been put into practical use. In addition, phthalocyanine pigments have different crystal types such as α-type, β-type, δ-type, and ε-type, and each has excellent properties such as clearness and high coloring power. Yes. In conventional color filters, these copper phthalocyanine pigments are dioxazine pigments C.I. I. In combination with Pigment Violet 23 and the like, high brightness and a wide color display area have been achieved.

  However, it has become difficult to achieve higher lightness and a wide color reproduction region with the increasing demand.

JP 2004-279617 A

Supervised by Kunihiro Ichimura, “State-of-the-art color filter process technology and chemicals”, CMC Publishing Co., Ltd., issued April 1, 2006, p. 79-83

  The present invention has been made in view of such a situation, and includes a blue coloring composition for a color filter capable of forming a color filter capable of high brightness and a wide color reproduction region, and a filter segment formed using the same. It is an object of the present invention to provide a color filter, and to provide a color display device equipped with the color filter.

  As a result of intensive studies to solve the above problems, the present inventors have obtained, as a colorant for a blue coloring composition for a color filter, a phthalocyanine blue pigment that has been conventionally used by the general formula (1). It has been found that high brightness and a wide color reproduction region can be achieved by using a combination of the expressed dyes, and the present invention has been made based on this finding.

  That is, the present invention relates to a blue coloring composition for a color filter, in which the colorant comprises at least a phthalocyanine blue pigment and a dye represented by the general formula (1).

  General formula (1)

[In General Formula (1), R1 represents N or CH, D represents an electron-donating group, A represents an electron-accepting group, R2 and R3 represent hydrogen, or a substituent having 1 to 6 carbon atoms, R2 and R3 may form a ring. ]

  In the present invention, the phthalocyanine blue pigment is C.I. I. Pigment blue 15: 6 and C.I. I. It is related with the blue coloring composition for color filters of the said invention which is at least 1 sort (s) chosen from CI pigment blue 15: 1.

  Moreover, this invention relates to the blue coloring composition for color filters of any one of the said invention characterized by including transparent resin.

  The present invention also relates to a blue coloring composition for a color filter according to any one of the above inventions, which comprises a monomer and / or a polymerization initiator.

  Further, the present invention provides a color filter having at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein at least one of the blue filter segments is for the color filter according to any one of the above inventions. The present invention relates to a color filter formed of a blue coloring composition.

  In the present invention, by combining a color filter formed from a blue coloring composition using at least a phthalocyanine blue pigment and a dye represented by the general formula (1) as a colorant, high brightness, a wide color display area, and a high contrast ratio are combined. A color display device having the above can be obtained.

Hereinafter, the present invention will be described in detail.
[First Form of Blue Coloring Composition for Color Filter of the Present Invention (Blue Pigment Paste for Color Filter or Blue Colored Ink Form)]
Of the preferred forms of the blue colored composition for color filters of the present invention, the first specific form is a blue colored composition for color filters comprising a pigment dispersion containing a colorant, a transparent resin, and a solvent. The colorant is a blue coloring composition for a color filter comprising at least a phthalocyanine blue pigment and a dye represented by the general formula (1). The blue colored composition of the first form is a blue colored composition (resist composition) for color filter or a blue composition for forming color filter (colored ink composition) of the third form of the present invention described later. Blue color composition (colored ink composition) that can be used as a colorant component (pigment paste) and that itself forms a blue filter segment of a color filter by selecting viscosity, materials used, and production method It can also be used as Hereinafter, other components such as a colorant, a transparent resin, a solvent, a dispersibility improver used as necessary, and a dispersion aid used in the blue coloring composition for a color filter according to the first embodiment of the present invention will be sequentially described. .

[Colorant]
As the colorant of the blue coloring composition, at least a phthalocyanine blue pigment and a dye represented by the general formula (1) are used. First, examples of the phthalocyanine blue pigment include C.I. I. Pigment Blue 5, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment Blue 16, Cobalt Phthalocyanine, Nickel Phthalocyanine, Zinc Phthalocyanine, Palladium Phthalocyanine, Platinum Phthalocyanine, and the like are mentioned. Among them, copper phthalocyanine blue pigments having ε-type and α-type structures are preferable. Such preferred pigments are specifically C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Blue 15: 1.

  Next, the dye represented by the general formula (1) will be described. Having an electron-donating group and an electron-accepting group at a specific position in the molecule is necessary for transmitting a specific wavelength and improving the brightness.

General formula (1)

  In the general formula (1), R1 represents N or CH, D represents an electron-donating group, A represents an electron-accepting group, R2 and R3 represent hydrogen or a substituent having 1 to 6 carbon atoms, R2 And R3 may form a ring.

The electron donating group is a substituent having an effect of increasing the charge density of an aromatic carbon atom to which the group is bonded, and specific examples include an amino group and a hydroxyl group. A substituent may be bonded to the amino group or the hydroxyl group directly or via a divalent linking group. Examples of the divalent linking group include —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —OCO—, —NHCO—, —OCOO— and the like.
As a substituent which may be bonded directly or via a divalent linking group,
A monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, and a monovalent aromatic heterocyclic group.

  Here, the monovalent aliphatic hydrocarbon group preferably refers to a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, a cyclo And an alkyl group.

Therefore, as the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, C1-C18 alkyl groups, such as a decyl group, a dodecyl group, a pentadecyl group, and an octadecyl group, are mentioned.

Examples of the alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1-decenyl group, 1 -An alkenyl group having 2 to 18 carbon atoms such as an octadecenyl group.

Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group and 1-octadecynyl group. Examples thereof include alkynyl groups having 2 to 18 carbon atoms.

In addition, the cycloalkyl group has a carbon number such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, 2-bornyl group, 2-isobornyl group, 1-adamantyl group. Examples thereof include 3 to 18 cycloalkyl groups.

Furthermore, the monovalent aromatic hydrocarbon group is preferably a monovalent monocyclic, condensed ring, or ring-aggregated aromatic hydrocarbon group having 6 to 30 carbon atoms. Here, as a monovalent monocyclic aromatic hydrocarbon group having 6 to 30 carbon atoms, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl And monovalent monocyclic aromatic hydrocarbon groups having 6 to 30 carbon atoms such as a group and a mesityl group.

Examples of the monovalent condensed ring aromatic hydrocarbon group include 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1-acenaphthyl group, 2-azurenyl group, 1-pyrenyl group, 2-triphenylyl group, 1-pyrenyl group, 2-pyrenyl group, 1-perylenyl group, 2-perylenyl group, 3-perenylenyl group, 2-trephenylenyl group, Examples thereof include monovalent condensed ring hydrocarbon groups having 10 to 30 carbon atoms such as 2-indenyl group, 1-acenaphthylenyl group, 2-naphthacenyl group, and 2-pentacenyl group.

The monovalent ring-aggregated aromatic hydrocarbon group has 12 carbon atoms such as o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, terphenylyl group, 7- (2-naphthyl) -2-naphthyl group and the like. ˜30 monovalent ring-assembled aromatic hydrocarbon groups.

In addition, as the monovalent aliphatic heterocyclic group, a monovalent fatty acid having 3 to 18 carbon atoms such as a 3-isochromanyl group, a 7-chromanyl group, a 3-coumarinyl group, a piperidino group, a morpholino group, and a 2-morpholino group. Group heterocyclic group.

Examples of the monovalent aromatic heterocyclic group include 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-benzofuryl group, 2-benzothienyl group, 2-pyridyl group, 3 Examples thereof include monovalent aromatic heterocyclic groups having 3 to 30 carbon atoms such as -pyridyl group, 4-pyridyl group, 2-quinolyl group, and 5-isoquinolyl group.

These substituents may be further substituted with other substituents directly or via the above-described divalent linking group, and these substituents may be bonded to each other to form a ring. good.

  The electron-accepting group is a substituent that has an effect of lowering the charge density of the aromatic carbon atom contained in the group. Specifically, the substituent is represented by a ketone group or a general formula (2). Is mentioned. R4 and R5 are the same as the groups that may be bonded to the amino group of the electron donating group.

Z ⁻ is an anion capable of forming a salt and can be appropriately selected as long as it is an ion having no coloration. Examples of monovalent anions include halogen ions such as chlorine and bromine, acetate ions, benzoate ions, nitrate ions, phosphotungstate ions, phosphomolybdate ions, phosphotungsten molybdate ions, silicon molybdate ions, and copper cyanide. Examples thereof include ferrate ions. Examples of the divalent anion include sulfate ion, carbonate ion, oxalate ion, methanesulfonate ion, toluenesulfonate ion and the like. Examples of trivalent anions include phosphate ions and borate ions.

General formula (2)

Here, specific examples of the structure of the dye represented by the general formula (1) are given.

Illustrative dye 1

Illustrative dye 2

Illustrative dye 3

Illustrative dye 4

Illustrative dye 5

Illustrative dye 6

Illustrative dye 7

Illustrative dye 8

Illustrative dye 9

Illustrative dye 10

Illustrative dye 11

Illustrative dye 12

Illustrative dye 13

Illustrative dye 14

The dyes exemplified here are available as reagents from reagent manufacturers.

  The dye represented by the general formula (1) has a transmittance of 90% or more in the 650 nm region in the transmission spectrum, a transmittance of 75% or more in the 600 nm region, and a transmittance of 20% or less in the 500 to 550 nm region. In the region of 400 nm, the transmittance is preferably 70% or more. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance is 10% or less in the region of 500 to 550 nm, and the transmittance is 75% in the region of 400 nm. That's it.

  The use ratio of the phthalocyanine blue pigment and the dye represented by the general formula (1) is preferably 10 to 150 parts by weight of the dye represented by the general formula (1) with respect to 100 parts by weight of the phthalocyanine blue pigment.

[Transparent resin]
The transparent resin preferably used for the blue coloring composition of the present invention is 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 transparent resin may be any of a thermoplastic resin, a thermosetting resin, and a photocurable resin, and is 30 to 500 weights based on the total weight of the pigment and the dye represented by the general formula (1). % Can be used. 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 epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  When the coloring composition is used in the form of an alkali developing type colored resist, 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 disperse the pigment preferably, 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 average molecular weight (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 average molecular weight of the sample. Furthermore, it calculates by converting into polyethylene by the conversion formula derived from the Mark-Houwink viscosity formula.

  The photocurable resin has a reactive substituent such as an isocyanate group, an aldehyde group, an epoxy group, and a carboxyl group in a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, and an amino group ( A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced by reacting a (meth) acrylic compound or cinnamic acid is preferably 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 a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A half-esterified product is also used.

〔solvent〕
The colored composition of the first aspect of the present invention is applied to a pigment carrier in order to sufficiently disperse the pigment in the pigment carrier, and to a dry film thickness of 0.2 to 5 μm on a substrate such as a glass substrate. In forming the filter segment, a solvent is contained in order to facilitate the formation of the coating film.

  Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 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-butylal 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 monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Recall monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether , Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl Tons, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, but dibasic acid ester and the like, not necessarily limited thereto. These solvents are used alone or in combination. When the colored composition according to the first form is used as a pigment paste such as the colored composition of the third form, the solvent is based on the total weight of the pigment and the dye represented by the general formula (1). Thus, it is preferably used in an amount of 800 to 4000% by weight.

[Dye derivative]
In the blue 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. A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Such organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more. When using a pigment derivative, the blending amount is preferably 0.001 to 40% by weight based on the total weight of the pigment and the pigment represented by the general formula (1), more preferably from the viewpoint of dispersibility. From the viewpoint of 0.1 to 30% by weight, heat resistance and light resistance, it is most preferably 0.5 to 25% by weight. When the blending amount of the dye derivative is less than 0.001% by weight with respect to the total weight of the pigment and the dye represented by the general formula (1), the dispersibility may be deteriorated. And light resistance may deteriorate.

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

  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 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 Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more. The blending amount of the resin-type dispersant is preferably 0.001 to 40% by weight based on the total weight of the pigment and the dye represented by the general formula (1), and more preferably from the viewpoint of dispersibility. From the viewpoint of 1 to 35% by weight, heat resistance and light resistance, it is most preferably 0.5 to 30% by weight. If the blending amount of the resin-type pigment dispersant is less than 0.001% by weight based on the total weight of the pigment and the dye represented by the general formula (1), the dispersibility may be deteriorated. When it exceeds, heat resistance and light resistance may deteriorate.

(Leveling agent)
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate Nonionic surfactants such as polyethylene glycol monolaurate; alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines; and fluorine-based and silicone-based surfactants.

[Curing agent, curing accelerator]
Moreover, in order to assist hardening of a thermosetting resin, a hardening | curing agent, a hardening accelerator, etc. may be included as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01 to 15 weight% is preferable with respect to the thermosetting resin whole quantity.

[Other additive components]
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total weight of the pigment and the dye represented by the general formula (1).

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The silane coupling agent is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total weight of the pigment and the dye represented by the general formula (1) in the coloring composition. It can be used in parts.

[Method for producing colored composition according to first embodiment]
The colored composition according to the first aspect of the present invention includes a colorant (a pigment paste when the colorant is supplied as a pigment paste), a transparent resin, a solvent, and other dye derivatives and dispersion aids as necessary. Is obtained by treating with a wet pulverizer. Examples of the wet pulverizer used in the present invention include an attritor, a sand mill, a dyno mill, a ball mill, a super apex mill, a spike mill, a coball mill, a diamond fine mill, a DCP mill, and an OB mill, or a homogenizer, myco Examples include media-type wet pulverizers such as Royder, Trigonal, Thrasher, Colloid Mill, Cavitron, Golator, Genus, and Claremix. The distribution method may be either circulation or path distribution. Furthermore, the coloring composition by the 1st form of this invention can also be manufactured by mixing the several coloring agent separately disperse | distributed finely.

[Removal of coarse particles]
The colored composition according to the first aspect of the present invention is a coarse particle of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove coarse particles and mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, the particle diameter of the particles in the colored composition is preferably 0.3 μm or less. In addition, the particle diameter here means the particle diameter measured by SEM.

[Second Form of Blue Composition for Color Filter of the Present Invention (Chip Form)]
The second form of the blue composition for a color filter of the present invention is a colored composition in the form of a chip containing a colorant and a thermoplastic resin, and the colorant comprises at least a phthalocyanine blue pigment, a general formula ( 1) The pigment | dye represented by is included.

[Method for producing colored composition according to second embodiment]
The coloring composition according to the second aspect of the present invention comprises a coloring agent and a thermoplastic resin, and optionally other components such as a pigment derivative and a dispersion aid, a Henschel mixer, a cooler mixer, a nauter mixer, a drum mixer, After mixing using a tumbler or the like, it is manufactured by heating and kneading with a Banbury mixer, a kneader, a two-roll mill, a single-screw extruder, a twin-screw extruder, etc., cooling and pulverizing. The pigment chip thus produced is refined as necessary using various grinding devices such as a hammer mill, a turbo crusher, an air jet mill and the like, and the first form of the pigment paste and the blue coloring composition for forming the blue filter segment ( Ink form) can be used as a colorant.

[Third Form of Blue Coloring Composition for Color Filter of the Present Invention (for example, Colored Resist Form)]
A third form of the blue coloring composition for a color filter of the present invention is a coloring composition containing a coloring agent, a transparent resin, a solvent, a monomer and / or a polymerization initiator, and the coloring agent is at least A blue composition comprising a phthalocyanine blue pigment and a dye represented by the general formula (1), which is the first embodiment of the present invention, itself used to form a blue filter segment of a color filter Further, a monomer and / or a polymerization initiator are included as essential components. Therefore, except for the components other than the monomer and / or the polymerization initiator in the blue coloring composition for the color filter of the third form, and further, if necessary, the composition components used are: Basically, it is not particularly different from the components used in the blue composition of the first form, which is itself used to form the blue filter segment of the color filter. For this reason, below, the monomer which is an arbitrary component, a polymerization initiator, and also the sensitizer used with these are demonstrated in a 1st form. In addition, when the blue coloring composition for color filters of the third form is formed using the blue coloring composition for color filters (pigment paste) of the first form as a colorant component, the first form Blue color composition for color filters (pigment paste), monomers, polymerization initiators, and transparent resins, solvents, leveling agents, storage stabilizers, silane coupling agents, etc. It is preferable that it is formed from these components. The polymerization initiator of the present invention includes a photopolymerization initiator and a thermal polymerization initiator.

〔monomer〕
The monomer of the present invention is a monomer that cures by ultraviolet rays, heat, or the like to form a transparent resin [so-called “oligomer” is also included in the “monomer” of the present invention. Are preferably used, and these may be used alone or in admixture of two or more. The blending amount of the monomer is preferably 5 to 400% by weight based on the total weight of the pigment and the dye represented by the general formula (1), and 10 to 300% by weight from the viewpoint of photocurability and developability. % Is more preferable.

  Examples of monomers that can be cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 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, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether (Meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (Meth) acrylates, ester acrylates, methylolated melamine (meth) acrylic acid esters, epoxy (meth) acrylates, urethane acrylates and other acrylic and methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxy Ethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) Examples include acrylamide, N-vinylformamide, acrylonitrile and the like, but are not necessarily limited thereto. These monomers that are cured by irradiation with active energy rays to form a transparent resin can be used alone or in admixture of two or more.

(Photopolymerization initiator)
In the colored composition for color filter in the third aspect of the present invention, a photopolymerization initiator is added as necessary in order to cure the composition by irradiation with ultraviolet rays and form a filter segment by a photolithographic method. Is done. Note that a photopolymerization initiator is also used when a photocurable resin is used as the transparent resin in the first embodiment. The blending amount when using the photopolymerization initiator is preferably 5 to 200% by weight based on the total weight of the pigment and the dye represented by the general formula (1), and is photocurable and developable. From the viewpoint of the above, it is more preferably 10 to 150% by weight.

  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-morpho Acetophenone photopolymerization initiators such as linopropan-1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, benzoylbenzoic acid Me , Benzophenone photopolymerization initiators such as 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthio Thioxanthone photopolymerization initiators such as xanthone and 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-bi (Trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) Triazines such as -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine And photopolymerization initiators, borate photopolymerization initiators, carbazole photopolymerization initiators, and imidazole photopolymerization initiators. The said photoinitiator can be used individually or in mixture of 2 or more types.

[Sensitizer]
Moreover, a sensitizer may be used with the said photoinitiator as needed. As the sensitizer, any conventionally known sensitizer for the photopolymerization initiator can be used. Specifically, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, Examples of the compound include 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and 4,4′-diethylaminobenzophenone, but are not limited thereto. 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.

(Thermal polymerization initiator)
When a thermosetting resin is used as the transparent resin, a thermopolymerization initiator may be included as necessary. Examples of the thermal polymerization initiator include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne-3, 1,4- Bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5- Di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylper-sec-octoate, tert-butylperpivalate, cumylper Bareto and tert- butyl hydroperoxide diethyl acetate, other azo compounds such as azobisisobutyronitrile, dimethyl azoisobutyrate, and the like.

[Method for producing colored composition according to third embodiment]
The coloring composition according to the third aspect of the present invention uses a colorant, a transparent resin, a solvent, and, if necessary, a pigment derivative using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. It is prepared by finely dispersing, and can be obtained by adding and mixing the monomer and / or polymerization initiator and, if necessary, other components described above by known means. In the colored composition according to the third aspect of the present invention, as described above, the blue colored composition (pigment paste) of the first form may be used as a colorant, and such a method is preferred. It is. In addition, several types of pigments are separately finely dispersed to prepare a pigment dispersion, which is then mixed, and further added with a monomer and / or a polymerization initiator and, if necessary, other components described above by known means. It can also be produced by mixing.

[Removal of coarse particles]
The colored composition according to the third aspect of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably 0.5 μm or more by means of centrifugation, a sintered filter, a membrane filter or the like. It is preferable to remove coarse particles and mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, the particle diameter of the particles in the colored composition is preferably 0.3 μm or less. In addition, the particle diameter here means the particle diameter measured by SEM.

[Color filter]
The color filter of the present invention is a color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein at least one of the blue filter segments is a blue color for a color filter of the present invention. It is formed from a coloring composition.

[Blue filter segment]
The blue filter segment of the color filter of the present invention contains at least a phthalocyanine blue pigment and a dye represented by the general formula (1) as a colorant as described above. Such a blue filter segment can be formed using the blue coloring composition for color filters of the present invention described above. As a formation method, any one of publicly known or well-known methods for forming a conventional color filter segment, such as a printing method, an ink jet method, and a photolithography method, may be employed depending on the composition of the blue coloring composition. .

  The dye represented by the general formula (1) has a high transmittance in the vicinity of 450 to 480 nm and a strong light absorption in the vicinity of 500 to 550 nm in the transmittance characteristic. It is possible to cut. Conventionally, in a display device using a cold cathode tube type backlight as a light source, a dioxazine pigment has been used as a colorant together with a copper phthalocyanine blue pigment in a blue coloring composition for forming a blue filter segment. Although good color developability can be obtained by cutting light in the region near 500 to 550 nm, dioxazine pigments are not capable of cutting light in the region from 500 to 550 nm. In order to form a blue filter segment using a blue coloring composition for a color filter using a copper phthalocyanine blue pigment and a dioxazine pigment, the film thickness of the color filter is increased in order to cut light in the region of 500 to 550 nm. There was a need. The dioxazine-based pigment has a light absorption larger than the region of 500 to 550 nm in the vicinity of 460 nm. For this reason, the transmittance near the peak near 460 nm also decreases due to the increase in thickness, and as a result, the brightness of the color filter decreases.

  On the other hand, by combining the dye represented by the general formula (1) with a copper phthalocyanine blue pigment, a color filter having a brightness and a color display region far superior to those of conventional color filter coloring compositions is obtained. It became possible. In order to reproduce colors at a relatively high density near standard areas such as sRGB and NTSC in the CIE chromaticity coordinates, the blue filter segment needs to have an optimum hue. In order to reproduce colors in the vicinity of the standard region, a certain amount of phthalocyanine blue pigment having high coloring power and high lightness is necessary. However, the dye represented by the general formula (1) is based on 100 parts by weight of phthalocyanine blue pigment. When the amount is more than 150 parts by weight, high brightness is exhibited, but a wide color display area cannot be achieved. On the other hand, when the amount of the dye represented by the general formula (1) is less than 10 parts by weight with respect to 100 parts by weight of the phthalocyanine blue pigment, a wide color display area can be achieved, but high brightness cannot be achieved. The phthalocyanine blue pigment used as the colorant of the present invention has a transmittance of 80% or more in the region of 450 nm in the transmission spectrum, a transmittance of 70% or more in the region of 500 nm, and a transmittance of 30 in the region of 550 to 600 nm. % Or less is preferred.

In order to achieve high brightness and a wide color display area, the present inventors have made extensive studies, and as a result, a color filter comprising a phthalocyanine blue pigment and a dye represented by the general formula (1) as a blue filter segment as described above. The conventional problem can be solved by using the blue coloring composition.

[Green filter segment]
The green filter segment of the color filter of the present invention contains a green pigment as a colorant. Examples of the green pigment include C.I. I. Pigment green 7, 10, 36, 37, 58 and the like.

  Moreover, a yellow pigment may be used in combination with the green filter segment as a colorant. Examples of 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, 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, 181 182, 185, 187, 188, 193, 194, 198, 199, 213, 214 and the like.

  In order to form the green filter segment of the color filter of the present invention, a green pigment and a yellow pigment as described above are used, for example, a transparent resin component, a solvent, and further, if necessary, a monomer, a polymerization initiator, and other blue coloring composition. Using the same material as used for forming, a green colored composition is manufactured by the same method as the blue colored composition, and using this green colored composition, the same method as the formation of the blue filter segment is performed. A green filter segment may be formed.

[Red filter segment]
The red filter segment of the color filter of the present invention contains a red pigment as a colorant. Examples of red pigments 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, and the like.

  Further, in the red filter segment of the color filter of the present invention, in addition to the red pigment, 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, 181 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, etc., may be used in combination.

  In order to form the red filter segment of the color filter of the present invention, the red pigment as described above and, if necessary, an orange pigment or a yellow pigment, for example, a transparent resin component, a solvent, and further, if necessary, a monomer or a polymerization initiator, In addition, a red colored composition is produced by the same method as the production of the blue colored composition using the same material as that used for forming the blue colored composition, and this red colored composition is used to produce a blue filter segment. What is necessary is just to form a red filter segment by the method similar to formation.

[Manufacture of color filters]
Below, the manufacturing method of the color filter using the coloring composition of this invention is demonstrated.
The color filter of the present invention includes a filter segment on a substrate, and can include, for example, a black matrix and red, green, and blue filter segments. The said filter segment can be formed on a board | substrate by apply | coating the coloring composition of this invention by a spin coat system or a die coat system, for example. At this time, each segment can be formed using a photolithography technique using a colored composition containing a monomer, a photopolymerization initiator, and the like. Each segment can also be formed by a printing method. As a printing method at this time, a conventional well-known printing method or an inkjet method can be used.

  As a substrate of the color filter, a substrate having a high transmittance for visible light, for example, a glass plate such as soda lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, polycarbonate, polymethyl methacrylate, polyethylene A resin plate such as terephthalate is used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

  When forming a filter segment, when using a photocurable coloring composition (coloring resist) containing a monomer, a photopolymerization initiator, etc., the coloring composition film is developed after exposure. As the developer, a known alkali developer conventionally used for developing a photosensitive resin, for example, an aqueous solution of sodium carbonate, sodium hydroxide or the like, or an organic alkali such as dimethylbenzylamine, triethanolamine or the like is used. Can do. Moreover, an antifoamer and surfactant can also be added to a developing solution. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  In order to increase the UV exposure sensitivity, after coating and drying the colored composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the 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. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the 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.

An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.
For example, in the case where a color filter is provided on the TFT substrate, the TFT substrate provided with 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 portion, the injection port is set. A liquid crystal display panel is manufactured by sealing and attaching a polarizing film or a retardation film to the outside of the substrate as necessary. If a color filter is formed on the counter substrate, the counter substrate on which the color filter is formed is bonded to the control substrate using a sealant, and liquid crystal is injected from an injection port provided in the seal portion. A liquid crystal display panel is manufactured by sealing the entrance and attaching a polarizing film or a retardation film to the outside of the substrate as necessary.

  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.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the following, “parts” means “parts by weight” unless otherwise specified.

First, the preparation of acrylic resin solutions used in Examples and Comparative Examples will be described.
(Preparation of acrylic resin solution)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. 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. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Addition to prepare an acrylic resin solution.

(Blue pigment dispersion 1)
Blue pigment as phthalocyanine pigment (Lionol Blue ES CI Pigment Blue 15: 6, manufactured by Toyo Ink Manufacturing Co., Ltd.) 11.0 parts, acrylic resin solution 40 parts, propylene glycol monomethyl ether acetate (PGMAC) 48.0 parts, resin type A mixture of 1.0 part of a dispersant (EFKA4300) was uniformly stirred and mixed, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. Then, it filtered with a 5.0 micrometer filter and produced the blue pigment dispersion 1. FIG.

(Blue pigment dispersions 2-3, red pigment dispersions 1-2, yellow pigment dispersion 1, green pigment dispersion 1, yellow pigment dispersion 2, purple pigment dispersion 1)
Except for using the pigments shown in Table 1, blue pigment dispersions 2-3 used for the blue coloring composition (resist), red pigment dispersions 1-2, yellow, in the same manner as in the preparation of blue pigment dispersion 1 above Pigment dispersion 1, green pigment dispersion 1, yellow pigment dispersion 2, and purple pigment dispersion 1 were prepared.

[Preparation of coloring composition for color filter (resist)]
(1) A blue colored composition (resist) for color filters (hereinafter sometimes referred to as “blue resist”) was prepared by the following procedure.
(Blue resist 1: coloring composition according to the third aspect of the present invention)
When the blue coloring composition (resist) is applied to the substrate, the blue dispersion 1 is expressed by the general formula (1) so that the CIE chromaticity coordinates are x = 0.135 and y = 0.141. Exemplified compound 1 is mixed as a pigment to obtain a pigment dispersion. This pigment dispersion is 60.0 parts, a photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan), dipentaerythritol. Pentaacrylate and hexaacrylate (“Aronix M400” manufactured by Toagosei Co., Ltd.) 4.2 parts, sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts, acrylic resin solution 11.0 parts, methoxypropyl Blue resist 1 was prepared by stirring and mixing so that 23.2 parts of acetate were uniform and filtered through a 1.0 μm filter.

(Blue resists 2 to 10: coloring composition according to the second embodiment of the present invention)
Blue resists 2 to 10 were produced in the same manner as the blue resist 1 except that the combination of pigment dispersions shown in Table 2 was used.
(Comparison blue resist 1)
When the blue coloring composition (resist) is applied to the substrate using the blue dispersion 1 and the purple dispersion 1, mixing is performed so that the CIE chromaticity coordinates are x = 0.135 and y = 0.141. A pigment dispersion was obtained, and 60.0 parts of this pigment dispersion, 1.2 parts of a photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan), dipentaerythritol pentaacrylate and hexaacrylate (Toagosei Co., Ltd.) "Aronix M400" made by 4.2), sensitizer ("EAB-F" made by Hodogaya Chemical Co., Ltd.) 0.4 part, acrylic resin solution 11.0 parts, and methoxypropyl acetate 23.2 parts become uniform. The mixture was stirred and mixed and filtered through a 1.0 μm filter to prepare a comparative blue resist 1.

(2) A red colored composition (resist) for color filters (hereinafter sometimes referred to as “red resist”) was prepared by the following procedure.
(Red resist)
When the red coloring composition (resist) is applied to the substrate, the red dispersion 1 and the red dispersion 2 and the yellow are mixed so that the CIE chromaticity coordinates are x = 0.640 and y = 0.330. Dispersion 1 was mixed to obtain a pigment dispersion. 60.0 parts of this pigment dispersion, 1.2 parts of a photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan), dipentaerythritol pentaacrylate and 4.2 parts of hexaacrylate ("Aronix M400" manufactured by Toagosei Co., Ltd.), 0.4 parts of sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.), 11.0 parts of acrylic resin solution, 23. methoxypropyl acetate. The mixture was stirred and mixed so that 2 parts were uniform, and filtered through a 1.0 μm filter to prepare a red resist.

(2) A green coloring composition (resist) for color filters (hereinafter sometimes referred to as “green resist”) was prepared by the following procedure.
(Green resist)
When the green coloring composition (resist) is applied to the substrate, the green dispersion 1 and the yellow dispersion 2 are mixed so that the CIE chromaticity coordinates are x = 0.300 and y = 0.600. A pigment dispersion was obtained, and 60.0 parts of this pigment dispersion, 1.2 parts of a photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan), dipentaerythritol pentaacrylate and hexaacrylate (Toagosei Co., Ltd.) "Aronix M400", 4.2 parts, sensitizer ("EAB-F", Hodogaya Chemical Co., Ltd.) 0.4 parts, acrylic resin solution 11.0 parts, methoxypropyl acetate 23.2 parts uniformly The mixture was stirred and mixed, and filtered through a 1.0 μm filter to produce a green resist.
[Example 1]
Using the spin resister on the 100 mm × 100 mm, 0.7 mm thick glass substrate, the CIE chromaticity coordinates are x = 0.640 and y = 0.330. Applied. After drying, striped pattern exposure was performed with an exposure device with an integrated light amount of 150 mJ, and development was performed with an alkaline developer for 90 seconds to form a striped red filter segment. The alkali developer was 0.15% by weight of sodium carbonate, 0.05% by weight of sodium hydrogen carbonate, 0.1% by weight of an anionic surfactant (“PERILEX NBL” manufactured by Kao) and 99.7% of water. Consists of% by weight. The coated substrate was heated and allowed to cool, and then the green resist was coated to a thickness such that x = 0.300 and y = 0.600 in the same manner as the red resist. After drying, a striped pattern adjacent to the red filter segment was exposed with an exposure machine and developed with an alkaline developer for 90 seconds to form a striped green filter segment.

Further, in the same manner as the red resist, the blue resist 1 was applied so as to have a transmittance of 6% at 550 nm. After drying, striped pattern exposure was performed with an exposure machine and development was performed with an alkaline developer for 90 seconds to form striped blue filter segments adjacent to the red and green filter segments. A color filter having filter segments in the form of stripes of three colors of red, green, and blue on a transparent substrate was obtained. In addition, the transmission spectrum of the blue segment part of the obtained coating film was measured using the microspectrophotometer ("OSP-SP100" by Olympus Optical Co., Ltd.). The results are shown in Table 3.
The thing with the high transmittance | permeability in 470 nm which is a blue region was judged to be high brightness.

[Examples 2 to 10, Comparative Example 1]
Color filters of Examples 2 to 10 and Comparative Example 1 were produced in the same manner as Example 1 using the blue resists 2 to 10 and the comparative blue resist 1 instead of the blue resist 1. In the same manner as in Example 1, the transmission spectrum of the blue filter segment portion was measured with a microspectrophotometer. The results are shown in Table 3.

  Comparing Examples 1 to 10 and Comparative Example 1, the resist containing the dye represented by the general formula (1) has a higher transmittance than the resist containing the dioxazine pigment that has been suitably used conventionally. It can be seen that it is advantageous for brightness. From this, it can be said that the coloring composition for color filters containing the phthalocyanine blue pigment and the dye represented by the general formula (1) is excellent.

Claims (5)

A blue coloring composition for a color filter, wherein the colorant comprises at least a phthalocyanine blue pigment and a dye represented by the general formula (1).
General formula (1)

[In General Formula (1), R1 represents N or CH, D represents an electron-donating group, A represents an electron-accepting group, R2 and R3 represent hydrogen, or a substituent having 1 to 6 carbon atoms, R2 and R3 may form a ring. ]   The phthalocyanine blue pigment is C.I. I. Pigment blue 15: 6 and C.I. I. The blue coloring composition for a color filter according to claim 1, which is at least one selected from CI Pigment Blue 15: 1.   The blue coloring composition for a color filter according to claim 1 or 2, comprising a transparent resin.   The blue coloring composition for a color filter according to any one of claims 1 to 3, comprising a monomer and / or a polymerization initiator.   The color filter blue color according to any one of claims 1 to 4, wherein at least one of the blue filter segments is at least one red filter segment, at least one green filter segment and at least one blue filter segment. A color filter formed from a coloring composition.