JP5540519B2 - Coloring composition for color filter and color filter - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a color filter coloring composition used for forming a filter segment constituting a color filter used in a color liquid crystal display device and a solid-state imaging device, and a color filter obtained using the color filter coloring composition. .

  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. Is a display device that performs display. By providing a color filter between these two polarizing plates, color display is possible, and in recent years it has come to be used in televisions, personal computer monitors, etc., so there is a demand for higher brightness and higher contrast for color filters. Is growing.

  The color filter is formed by forming a colored layer directly or through a passivation film such as a silicon nitride film on a transparent substrate such as glass or a driving substrate on which a thin film transistor (TFT) is disposed. It consists of fine band (striped) filter segments of different colors or more arranged in parallel or intersecting, or fine filter segments arranged in a fixed arrangement. 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.

  The liquid crystal used in such a liquid crystal display device is easily affected by the electrical characteristics of members such as a color filter inherent in the liquid crystal display device, and adversely affects liquid crystal orientation disorder and switching performance due to liquid crystal contamination. Display defects may become a problem. In order to solve such a problem, the color layer of the color filter is required to have insulation, and it is necessary to increase the insulation by increasing the film thickness or to form a color film having a low dielectric constant. In order to solve such a problem, a method of selecting a dielectric loss tangent of two layers obtained by laminating an overcoat layer in a color layer of a green (green) pixel within a specific range has been studied (see Patent Document 1). .

  In particular, a colored layer is formed directly or via a passivation film such as a silicon nitride film on a driving substrate on which a thin film transistor (TFT), which has recently been attracting attention, and a substrate on which the colored layer is formed. In a method in which a transparent electrode for driving a liquid crystal is bonded to a substrate formed by vapor deposition or sputtering (see Patent Document 2), a colored layer is directly formed on a driving substrate on which a thin film transistor (TFT) is disposed. Since the pasting process as in the past is not necessary to form the pixel and the pixel aperture ratio (aperture ratio) can be greatly increased, it is possible to achieve high brightness and low power consumption, but Due to the mechanism, there is a problem that it is more susceptible to the electrical characteristics of the color filter.

  As a method for solving such a problem, a method using a specific initiator (see Patent Document 3) and the like have been disclosed, but the electrical characteristics derived from the members of the color filter are sufficiently improved. The current situation is that it has not been broken.

JP 2004-117537 A JP 2004-94263 A JP 2001-324611 A

  The present invention relates to a color filter in which the electrical properties of the colored layer do not adversely affect the alignment disorder of the liquid crystal and the switching performance, and the colored layer on the driving substrate of the thin film transistor (TFT) type color liquid crystal display device. Another object of the present invention is to provide a color filter coloring composition and a color filter capable of forming a color filter having excellent electrical characteristics.

The subject includes a copolymer (A) of a maleic anhydride and one or more types of ethylenically unsaturated monomers other than maleic anhydride, a pigment, a binder resin (B), an active energy ray polymerizable monomer, and contains an active energy ray polymerization initiator, the weight ratio of the copolymer (a) and the binder resin (B) (a) :( B ) is 5: 95 to 70: I 30 range der of And the binder resin (B) contains an alkali-soluble resin having a hydroxyl group .

  In the present invention, the one or more ethylenically unsaturated monomers other than maleic anhydride are monomers selected from the group consisting of styrene, α-methylstyrene, and indene. The present invention relates to a coloring composition for a color filter.

  The color filter coloring composition is characterized in that the content of the copolymer (A) is 10 to 20% by weight based on the solid content weight in the color filter coloring composition.

  The active energy ray polymerization initiator is a sulfonium organoboron complex or an oxosulfonium organoboron complex represented by the general formula (1), and relates to the coloring composition for a color filter according to any one of claims 1 to 6. .

 General formula (1):

(In general formula (1),
R ¹¹ is a benzyl group, an optionally substituted benzyl group, a phenacyl group, an optionally substituted phenacyl group, an aryloxy group, an optionally substituted aryloxy group, an alkenyl group Or an alkenyl group which may have a substituent,
R ¹² and R ¹³ are each independently the same as R ¹¹ or different from R ¹¹ and may have an alkyl group, an optionally substituted alkyl group, an aryl group, or a substituent. Good aryl group, aralkyl group, aralkyl group which may have a substituent, alkynyl group, alkynyl group which may have a substituent, alicyclic group, alicyclic group which may have a substituent, alkoxy group , An alkoxy group that may have a substituent, an alkylthio group, an alkylthio group that may have a substituent, an amino group, an amino group that may have a substituent, or R ¹² and R ¹³ may be mutually A linked ring structure,
R ¹⁴ is an oxygen atom or a lone pair,
X ⁻ is any anion. )
Further, the present invention relates to the coloring composition for a color filter, wherein X ⁻ in the general formula (1) is a borate represented by the following general formula (2).

  General formula (2):

[In general formula (2),
R ²¹ , R ²² , R ²³ , and R ²⁴ are each independently an alkyl group, an alkyl group that may have a substituent, an aryl group, an aryl group that may have a substituent, an aralkyl group, or a substituent. An aralkyl group, an alkenyl group, or an alkenyl group that may have a substituent. (However, all of R ²¹ , R ²² , R ²³ , and R ²⁴ do not become an aryl group or an aryl group that may have a substituent.)]

  In addition, the present invention relates to the color filter coloring composition, wherein the solvent contains cyclohexyl acetate.

  Furthermore, the present invention relates to the color filter coloring composition characterized by containing a tertiary phosphine compound.

  The tertiary phosphine compound is triphenylphosphine, and the present invention relates to the color filter coloring composition.

Furthermore, as a dispersant,
Hydroxyl group in a vinyl copolymer produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule, and having two hydroxyl groups at one end region And a polyester dispersant obtained by reacting an acid anhydride group in tetracarboxylic dianhydride with the color composition for a color filter.

  Further, the present invention relates to the coloring composition for a color filter, wherein the tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride.

  Furthermore, it is related with the color filter characterized by including the filter segment formed using the said coloring composition for color filters.

  The present invention also relates to a color filter comprising a filter segment in which a colored layer is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device using the colored composition for color filter.

  Since the colored layer formed using the colored composition for color filter of the present invention exhibits low dielectric constant characteristics and low dielectric loss tangent, it is possible to provide a color filter that does not adversely affect electrical characteristics.

The colored composition for a color filter of the present invention comprises a copolymer (A), a pigment, a binder resin (B), an active energy of maleic anhydride and one or more ethylenically unsaturated monomers other than maleic anhydride. A linear polymerizable monomer and an active energy ray polymerization initiator are contained , and the weight ratio (A) :( B) of the copolymer (A) to the binder resin (B) is from 5:95 to 70: The greatest feature is that the binder resin (B) is in the range of 30 and contains an alkali-soluble resin having a hydroxyl group .

  First, the color filter coloring composition of the present invention will be described in detail.

  In the present application, “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, or “(meth) acrylamide” When expressed, unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, “acryloyl”, respectively. It shall represent “oxy and / or methacryloyloxy” or “acrylamide and / or methacrylamide”.

[Copolymer of maleic anhydride and one or more ethylenically unsaturated monomers other than maleic anhydride (A)]
Each component of the copolymer (A) used for this invention is demonstrated.

As an ethylenically unsaturated monomer other than maleic anhydride, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), 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, iso Linear or branched alkyl (meth) acrylates such as myristyl (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) ) Acrylate, 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 an aromatic ring of
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, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acrylic Leyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, ethylene oxide modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, ω-carboxypolycaprolactone (meth) acrylate, etc. (Meth) acrylates having a carboxyl group of
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) acrylate, or glycerol (meth) acrylate (Meth) acrylates having a hydroxyl group such as
Olefin having an aromatic ring such as styrene, α-methylstyrene, indene, acetylnaphthylene, divinylbenzene, or bisbenzocyclobutene,
Fatty acid vinyls such as vinyl acetate and vinyl propionate,
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
Vinyl ethers having a hydroxyl group such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, or 2- (or 3- or 4-) hydroxybutyl vinyl ether,
Allyl ethers having a hydroxyl group such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, or 2- (or 3- or 4-) hydroxybutyl allyl ether,
(Meth) acrylamides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine ,
(Meth) acrylamides having a hydroxyl group such as N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl), or (meth) acrylamide ,
N, such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, or N, N-diethylaminopropyl (meth) acrylate Alkyl (meth) acrylates having an N-dialkylamino group, or
N, such as N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, or N, N-diethylaminopropyl (meth) acrylamide (Meth) acrylamides having an N-dialkylamino group,
These can be used alone or in combination of two or more, but are not necessarily limited thereto.

  Among these, a copolymer of maleic anhydride and an olefin having a benzene ring selected from the group consisting of styrene, α-methylstyrene, and indene has an extremely high molecular weight as shown in the following general formula (3). Since it has many repeating units with small polarity, the dielectric constant is low, which is preferable from the viewpoint of electrical characteristics.

  General formula (3):

[In General Formula (3), R ⁴¹ is a hydrogen atom or —CH ₃ , and R ⁴² and R ⁴³ are a hydrogen atom, or —CH ₂ — in which R ⁴² and R ⁴³ are combined. It is. ]
The maleic anhydride copolymerized with the ethylenically unsaturated monomer has an acid anhydride group, so that it can be used in combination with the binder resin (B) so that the coating film has good curability and developability. A composition can be formed.

  The molar ratio of maleic anhydride to one or more ethylenically unsaturated monomers other than maleic anhydride is from 1:10 to one or more ethylenically unsaturated monomers other than maleic anhydride: maleic anhydride. The ratio is preferably 1: 0.5, and more preferably 1: 8 to 1: 1 due to the effect on the developability and electrical characteristics of the color filter coloring composition.

As a commercially available copolymer (A) that can be used in the present invention,
“SMA1000”, “SMA2000”, “SMA3000”, “SMA EF30”, “SMA EF40”, “SMA EF60”, “SMA EF80” and the like (manufactured by Sartomer Japan) are included, but are not limited thereto. Arbitrary copolymer (A) can be used without these, and these can also be used individually or in mixture of 2 or more types.

  The content of the copolymer (A) is preferably 10 to 20% by weight based on the solid content weight in the color filter coloring composition. When the content of the copolymer (A) is less than 10% by weight, it is difficult to obtain an effect of improving electrical characteristics by addition, and when it is more than 20, there may be a problem in dispersion stability, development residue, and the like. is there.

[Binder resin (B)]
The binder resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. For example, the binder resin is a thermoplastic resin, a thermosetting resin, or a photosensitive resin. Resin. Especially, it is preferable that binder resin (B) contains alkali-soluble resin, and it is more preferable that the said alkali-soluble resin has a hydroxyl group.

By using this alkali-soluble resin, when the filter segment is formed by alkali development, the developability that cannot be achieved by using only the copolymer (A) in the present invention and the residue after development are improved. Can be expected.
Furthermore, by containing an alkali-soluble resin having a hydroxyl group, the characteristics of the present invention, such as a glass or the like by a crosslinking reaction between the acid anhydride group with the copolymer (A) and the hydroxyl group of the binder resin (B). Adhesion to a transparent substrate or a driving substrate provided with a thin film transistor (TFT) can be improved.

  Examples of the thermoplastic resin that can be used in the present invention include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyvinyl acetate. , Polyurethane resins, polyester resins, acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, 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.

  As the photosensitive resin, a (meth) acrylic compound or cinnamic acid having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group is used. Resins in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reaction are used. In addition, polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer are half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  The alkali-soluble resin is a resin that dissolves in an aqueous alkali solution, and has, for example, a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000, having an acidic functional group such as a carboxyl group or a sulfone group. Resin. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic functional group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or an isobutylene / (anhydrous) maleic acid copolymer etc. are mentioned. Further, the copolymer (A) of maleic anhydride and one or more kinds of ethylenically unsaturated monomers other than maleic anhydride may be used as they are, or these water or alcohol adducts may be used. Among them, at least one resin selected from an acrylic resin having an acidic functional group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic functional group, is preferably used because of its high heat resistance and transparency. It is done.

  Among the alkali-soluble resins, it is preferable that the ethylenically unsaturated monomer constituting the resin has a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate. 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, or a caprolactone adduct of these monomers can be used.

  By using such an alkali-soluble resin having a hydroxyl group, the acid anhydride portion of maleic anhydride and the hydroxyl group of the binder resin (B) in the copolymer (A) in the present invention are esterified by heating in forming a color filter. Crosslinking can be achieved by an exchange reaction, and adhesion to a transparent substrate such as glass or a driving substrate on which a thin film transistor (TFT) is arranged can be improved.

Although there is no restriction | limiting in particular about content of the alkali-soluble resin which has a hydroxyl group, It is preferable that it is 0 to 90 weight% and 10 to 80 weight% with respect to the total amount of binder resin (B). This is because when the content is more than 90% by weight, the dispersibility stability of the color filter coloring composition may be deteriorated.
The weight ratio (A) :( B) of the copolymer (A) and the binder resin (B) in the present invention is preferably in the range of 5:95 to 70:30. When the ratio of the copolymer (A) is less than 5, it is difficult to obtain an effect of improving electrical characteristics by addition, and when it is more than 60, the hydrophobicity increases, and other components in the color filter coloring composition. As a result, there may be a problem in dispersion stability and adhesion to a transparent substrate such as glass or a driving substrate on which a thin film transistor (TFT) is disposed.

[Pigment]
As a pigment contained in the coloring composition for a color filter of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used.

  Below, the specific example of the organic pigment which can be used for the coloring composition for color filters of this invention is shown with a color index number.

  For example, CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, may be used as a coloring composition for a red color filter to form a red filter segment. 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, Red pigments such as 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272, or 279 can be used. A yellow pigment or an orange pigment can be used in combination with the coloring composition for a red color filter.

  Examples of the coloring composition for yellow color filter for forming the yellow filter segment include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, Yellow pigments such as 67, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, or 214 Can be used.

  For example, an orange pigment such as CI Pigment orange 36, 43, 51, 55, 59, 61, 71, or 73 can be used as the coloring composition for the orange color filter for forming the orange filter segment. .

  As a coloring composition for a green color filter for forming a green filter segment, for example, a green pigment such as C.I. Pigment Green 7, 10, 36, 37, or 58 can be used. The yellow pigment can be used in combination with the coloring composition for a green color filter.

  Examples of the coloring composition for blue color filter for forming the blue filter segment include CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, Blue pigments such as 64 or 80 can be used. Purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, or 50 can be used in combination with the coloring composition for the blue color filter.

  For example, CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, or 81 is used as a coloring composition for forming a cyan filter segment. Pigments can be used.

  Examples of the magenta color filter coloring composition for forming a magenta color filter segment include purple pigments and red pigments such as CI Pigment Violet 1 or 19, or CI Pigment Red 81, 144, 146, 177, or 169. Can be used. A yellow pigment can be used in combination with the coloring composition for a magenta color filter.

  Inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. Examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

  The coloring composition for a color filter of the present invention may contain a dye within a range that does not decrease heat resistance for color matching.

[Pigment dispersant]
When dispersing the pigment, a pigment dispersant such as a dye derivative, a resin-type pigment dispersant, or a surfactant can be used as appropriate. Since the pigment dispersant is excellent in pigment dispersion and has a large effect of preventing reaggregation of the pigment after dispersion, a color filter excellent in transparency can be obtained. The pigment dispersant can be used in an amount of 0.1 to 30 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 basic derivative is particularly preferable, and the basic derivative is a compound represented by the following general formula (4), which is a derivative having a specific parent skeleton having a basic group. Although it will not specifically limit if it is a pigment derivative which has a basic group, The pigment derivative which has the triazine ring skeleton which has a basic group shown by following General formula (4) can be used conveniently.

  General formula (4):

P-Lm
[In General Formula (4), P is an m-valent organic pigment residue, an anthraquinone skeleton, an acridone skeleton, or a triazine skeleton, m is an integer of 1 to 4, and L is a general formula ( 5) A substituent selected from the group represented by (6) or (7). ]

  General formula (5):

  General formula (6):

  General formula (7):

[In the general formulas (5) to (7),
X _{is, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y ⁰ is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁹ —Z—NR ¹⁰ —, or a direct bond;
R ⁹ and R ¹⁰ are each independently a hydrogen bond, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or A phenyl group which may have a substituent,
Z is an alkylene group which may have a substituent, or an arylene group which may have a substituent,
R ¹ and R ² are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, or R ¹ and R ² together are a heterocyclic ring which may have a substituent, further containing a nitrogen, oxygen or sulfur atom;
R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 to carbon atoms that may have a substituent. 20 alkenyl group, an arylene group having 6 to 20 carbon atoms which may have a substituent,
R ⁷ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms,
R ⁸ is a substituent represented by the general formula (5) or a substituent represented by the general formula (6);
Q is a hydroxyl group, an alkoxyl group, a substituent represented by the above general formula (5), or a substituent represented by the above general formula (6). ]

  Examples of the amine component used for forming the substituents represented by the general formulas (5) to (7) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethyl. Propylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine , Dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadeci Amine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N , N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopen Ruamine, N, N-methyl-laurylaminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonicopetinate, Isonicopetic acid Ethyl, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, -Aminopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, etc. Is mentioned.

  The pigment derivative, anthraquinone derivative, and acridone derivative having a basic substituent of the present invention can be synthesized by various synthetic routes. For example, after introducing substituents represented by the following general formulas (8) to (11) into an organic dye, anthraquinone, or acridone, the substituents represented by the general formulas (5) to (7) react with the above substituents. The amine component forming the group, for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3 , 5-triazin-2-ylamino] aniline and the like.

Formula (8): —SO ₂ Cl
Formula (9): -COCl
Formula (10): —CH ₂ NHCOCH ₂ Cl
Formula (11): —CH ₂ Cl

  In the reaction of the substituents of the general formulas (8) to (11) with the amine component, a part of the substituents of the general formulas (8) to (11) are hydrolyzed and chlorine is substituted with a hydroxyl group. It may be mixed. In that case, the general formula (8) and the general formula (9) are a sulfonic acid group and a carboxylic acid group, respectively. Or a salt with a monoamine.

  Further, when the organic dye is an azo dye, the substituent represented by the general formulas (5) to (7) is introduced into the diazo component or the coupling component in advance, and then the coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

  The triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by general formulas (5) to (7) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N- It can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  In the pigment composition of the present invention, the amount of the pigment derivative having a base substituent is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, most preferably 5 to 25 parts per 100 parts by weight of the pigment. Parts by weight. When the basic derivative is less than 1 part by weight relative to 100 parts by weight of the pigment, the dispersibility may be deteriorated, and when it exceeds 50 parts by weight, the heat resistance and light resistance may be deteriorated. Among these, those having a triazine structure in the basic substituent are preferable from the viewpoint of dispersion stability.

(Resin type pigment dispersant)
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 adsorbs to the pigment to stabilize the dispersion of the pigment on the pigment carrier. It works.

As a resin type pigment dispersant,
Polyvinyl-based, polyurethane-based, polyester-based, polyether-based, formalin-condensed-based, silicone-based, or a composite polymer thereof.
Examples of pigment affinity sites include polar groups such as carboxyl groups, hydroxyl groups, phosphate groups, phosphate ester groups, sulfonate groups, hydroxyl groups, amino groups, quaternary ammonium bases, or amide groups, or polyethylene oxide and polypropylene oxide. Or a hydrophilic polymer chain such as a composite system thereof.
Examples of the site compatible with the dye carrier include a long-chain alkyl chain, a polyvinyl chain, a polyether chain, or a polyester chain.

Specifically, as a resin-type pigment dispersant,
Styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, poly (meth) acrylate, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid alkyl ester Copolymer, (meth) acrylic acid-polyvinyl-based macromer copolymer, phosphoric ester group-containing acrylic resin, aromatic carboxyl group-containing acrylic resin, polystyrene sulfonate, acrylamide- (meth) acrylic acid copolymer, carboxymethylcellulose An anionic resin type pigment dispersant such as polyurethane having a carboxyl group, formalin condensate of naphthalene sulfonate, or sodium alginate;
Nonionic resin-type pigment dispersants such as polyvinyl alcohol, polyalkylene polyamine, polyacrylamide, or polymer starch; or
Polyethyleneimine, aminoalkyl (meth) acrylate copolymer, polyvinylimidazoline, polyurethane having amino group, reaction product of poly (lower alkyleneimine) and polyester having free carboxyl group, or cationic resin type pigment such as satkinsan A dispersing agent is mentioned, These can be used individually or in mixture of 2 or more types.

As a commercially available resin-type pigment dispersant,
Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2090, 2091, 2164, or 2163, or Anti-Terra-U, 203, or 204, or BYK-P104, P104S, or 220S, or Lactimon, or Lactimon- Resin-type pigment dispersant manufactured by Big Chemie, such as WS or Bykumen;
SOLPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, or 53095 Nippon Lubrizol resin type pigment dispersant; or
EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, or 1503 Examples include resin-type pigment dispersants manufactured by Fuka Chemicals, etc., but are not limited thereto, and any resin-type pigment dispersant can be used, and these may be used alone or in admixture of two or more. it can.

  Among them, a preferable resin type dispersant is produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule described in WO2008 / 007776. A polyester dispersant obtained by reacting a hydroxyl group in a vinyl copolymer having two hydroxyl groups in the terminal region with an acid anhydride group in tetracarboxylic dianhydride is preferable. More preferably, the polyester dispersant is characterized in that the tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride. Coloring compositions for color filters using these polyester dispersants are not only excellent in pigment dispersion stability, but also can reduce the dielectric loss tangent, and are therefore less susceptible to electrical characteristics. As a method for synthesizing these resin-type dispersants, they can be synthesized using the method described in WO2008 / 007776.

(Surfactant)
As surfactant,
Polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, lauryl Anionic surfactants such as ammonium sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, or polyoxyethylene alkyl ether phosphate;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, or polyethylene glycol monolaurate;
Chaotic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adducts;
Examples include alkylbetaines such as alkyldimethylaminoacetic acid betaines; or amphoteric surfactants such as alkylimidazolines. These may be used alone or in admixture of two or more.

[solvent]
In the coloring composition for a color filter of the present invention, a pigment is sufficiently dispersed in a pigment carrier and applied on a transparent substrate such as glass so that a dry film thickness is 0.2 to 5 μm to form a filter segment. A solvent can be included to facilitate the process.
As a solvent, for example,
1,2,3-trichloropropane, 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, 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-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-die Benzene, 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, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene Glycol monomethyl A 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 glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, Acetone 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 ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, And dibasic Ester and the like, can be used alone or in combination.

  Preferably, by containing at least cyclohexyl acetate, a colored layer using the colored composition for a color filter in the present invention can be obtained with excellent flatness.

  The content of cyclohexyl acetate is 3 to 35% by weight, preferably 5 to 25% by weight, based on the total amount of the color filter coloring composition. When the content of cyclohexyl acetate exceeds 35% by weight, when the applied coating film is prebaked, the organic solvent does not sufficiently evaporate and remains in the dried coating film. This is because there is a possibility that (sex) may remain.

[Active energy ray polymerizable monomer]
The active energy ray polymerizable monomer contained in the coloring composition for a color filter of the present invention is a compound having an ethylenically unsaturated double bond that is cured by irradiation with active energy rays to produce a transparent resin. This means that the monomer includes a low polymer having an average molecular weight of less than 1000, generally called an oligomer, and having an ethylenically unsaturated double bond.

As an active energy ray polymerizable monomer,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), 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, iso Linear or branched alkyl (meth) acrylates such as myristyl (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, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl Carboxyl groups such as hexahydrophthalate, 2- (meth) acryloyloxypropylhexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, or ω-carboxypolycaprolactone (meth) acrylate (Meth) acrylates having;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl Phthalate, 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) acrylate, or having a hydroxyl group such as glycerol (meth) acrylate (meth) acrylates;
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, or 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, 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 di Glycidyl ether- (meth) acrylic acid adduct, propylene oxide-modified bisphenol A diglycidyl ether- (meth) acrylic acid adduct, bisphenol F diglycidyl ether- (meth) acrylic acid adduct, epichlorohydride -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- (meta ) 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 adduct, cresol novolac Type epoxy resin- (meth) acrylic acid adducts or other epoxy resins- (meth) acrylic acid adducts and other 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, and 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.

[Active energy ray polymerization initiator]
When the colored composition is cured by ultraviolet irradiation, an active energy ray polymerization initiator or the like is added to the colored composition for color filter.

As an active energy ray polymerization initiator,
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-based active energy ray polymerization initiator;
Benzoin-based active energy ray polymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal;
Benzophenone-based active energy ray polymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, or 4-benzoyl-4′-methyldiphenyl sulfide;
Thioxanthone-based active energy ray polymerization initiators 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-based active energy ray polymerization initiators such as triazine;
Borate-based active energy ray polymerization initiators;
A carbazole-based active energy ray polymerization initiator; or
An imidazole-based active energy ray polymerization initiator or the like is used.

  Among these, it is preferable to use a sulfonium organic boron complex or an oxosulfonium organic boron complex represented by the general formula (1).

  General formula (1):

(In general formula (1),
R ¹¹ is a benzyl group, an optionally substituted benzyl group, a phenacyl group, an optionally substituted phenacyl group, an aryloxy group, an optionally substituted aryloxy group, an alkenyl group Or an alkenyl group which may have a substituent,
R ¹² and R ¹³ are each independently the same as R ¹¹ or different from R ¹¹ and may have an alkyl group, an optionally substituted alkyl group, an aryl group, or a substituent. Good aryl group, aralkyl group, aralkyl group which may have a substituent, alkynyl group, alkynyl group which may have a substituent, alicyclic group, alicyclic group which may have a substituent, alkoxy group , An alkoxy group that may have a substituent, an alkylthio group, an alkylthio group that may have a substituent, an amino group, an amino group that may have a substituent, or R ¹² and R ¹³ may be mutually A linked ring structure,
R ¹⁴ is an oxygen atom or a lone pair,
X ⁻ is any anion. )

More preferably, it is an active energy ray polymerization initiator in which X ⁻ is a borate represented by the following general formula (2), and by using such an active energy ray polymerization initiator, the electrical properties of the color filter of the present invention are as follows. The characteristic effect becomes more excellent.

  General formula (2):

[In general formula (2),
R ²¹ , R ²² , R ²³ , and R ²⁴ are each independently an alkyl group, an alkyl group that may have a substituent, an aryl group, an aryl group that may have a substituent, an aralkyl group, or a substituent. An aralkyl group, an alkenyl group, or an alkenyl group that may have a substituent. (However, all of R ²¹ , R ²² , R ²³ , and R ²⁴ do not become an aryl group or an aryl group that may have a substituent.)]

  As means for synthesizing these active energy ray polymerization initiators, methods described in JP-A-5-213861, JP-A-5-255347, JP-A-8-15521 and the like are known.

  The active energy ray polymerization initiator can be used in an amount of 5 to 200% by weight, preferably 10 to 150% by weight, based on the weight of the pigment in the color filter coloring composition.

These active energy ray polymerization initiators are used alone or in combination of two or more, but as a sensitizer,
α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, A compound such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone or 4,4′-diethylaminobenzophenone can also be used in combination.

  The content of the sensitizer can be used in an amount of 0.1 to 60% by weight based on the weight of the active energy ray polymerization initiator in the colored composition.

[Additive]
As other additives, for example, as a storage stabilizer,
Quaternary ammonium chlorides such as benzyltrimethylammonium chloride or diethylhydroxyamine hydrochloride;
Organic acids such as lactic acid or oxalic acid;
Methyl ester of the organic acid;
pyrocatechol, such as t-butyl pyrocatechol;
An organic phosphine such as tributylphosphine, triphenylphosphine, tetraethylphosphine, or tetraphenylphosphine; or
Examples thereof include phosphite.

  Among them, by using a tertiary phosphine compound, more preferably triphenylphosphine, the effect on the low dielectric constant of the colored composition for a color filter in the present invention is excellent.

[Adjustment of coloring composition]
The color filter coloring composition can be prepared as a solvent developing type or alkali developing type color filter coloring composition. The coloring composition for a solvent developing type or alkali developing type color filter is generally composed of a binder resin (B) which is a thermoplastic resin, a thermosetting resin or a photosensitive resin, and an active energy ray polymerizable monomer. The pigment is dispersed in a composition containing an active energy ray polymerization initiator and an organic solvent.

  The coloring composition for a color filter of the present invention comprises a pigment or a pigment composition containing two or more types of pigments (hereinafter abbreviated as “pigment composition”), one or more types of ethylenic acid other than maleic anhydride and maleic anhydride. A copolymer with a saturated monomer (A), a binder resin (B), and, if necessary, a solvent, other pigment dispersants, additives and the like are mixed, and a three-roll mill, a two-roll mill, a kneader The pigment dispersion is prepared by dispersing the pigment composition in the varnish by dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, or attritor, and then the pigment dispersion, active energy ray polymerization Monomer, active energy ray polymerization initiator, if necessary, solvent, copolymer of maleic anhydride and one or more ethylenically unsaturated monomers other than maleic anhydride ( ), It can be prepared by mixing other pigment dispersing agent, and additives.

  It can also be produced by mixing several types of pigments separately dispersed on a pigment carrier. The active energy ray polymerization initiator may be added at the stage of preparing the color filter coloring composition, or may be added later to the prepared color filter coloring composition.

  The coloring composition for a color filter of the present invention is a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, more preferably a coarse particle of 0.5 μm or more by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove the mixed dust.

[Color filter manufacturing method]
Next, the manufacturing method of the color filter using the coloring composition for color filters 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 filter segment is formed on the substrate by applying the coloring composition of the present invention by a spin coat method or a die coat method.

  As a substrate for the color filter, glass plates such as soda lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, etc., which have high transmittance for visible light, and resins such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. A plate 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 for driving the liquid crystal after forming the panel.

  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. An antifoaming agent or a surfactant can also be added to the developer.

  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 UV exposure sensitivity, after applying and drying the above color filter coloring composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. Ultraviolet exposure can also be performed after forming a film.

  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. Examples of the black matrix include, but are not limited to, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed. 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.

  Here, a method for forming a colored layer on the TFT substrate will be described. First, on the surface of the TFT substrate or on the surface of the substrate on which a passivation film such as a silicon nitride film is formed on the surface of the driving substrate, a light shielding layer is formed so as to divide the pixel forming portion as necessary. After forming and applying a colored composition in which a pigment is dispersed on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, this coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked, whereby the pixel pattern has a predetermined arrangement. An arranged pixel array is formed. The photomask used at that time is provided with a pattern for forming a through hole or a U-shaped depression in addition to a pattern for forming a pixel.

  As the TFT substrate used for forming the colored layer, the same substrate as that of the color filter described above can be used, and these substrates include chemical treatment with a silane coupling agent, plasma treatment, ion plate, and the like. Appropriate pretreatments such as coating, sputtering, gas phase reaction, and vacuum deposition can also be performed. When the coloring composition is applied to the substrate, the same type as that of the above-described color filter substrate can be used. The coating thickness is preferably 0.1 to 10 μm, more preferably 0.5 to 6.0 μm, as the film thickness after drying.

  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.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter such as.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “part” means “part by weight”.

  Prior to Examples, finer pigments used in Examples and Comparative Examples, copolymers (A) of maleic anhydride and one or more types of ethylenically unsaturated monomers other than maleic anhydride, binder resins (B) A method for producing an acrylic resin solution, a polyester dispersant, and an active energy ray polymerizable initiator will be described. The molecular weight of the resin is HLC-8220GPC (manufactured by Tosoh Corporation) as a device, TSK-GEL SUPER HZM-N is connected in series as a column, and the polystyrene-converted weight average is measured using THF as a solvent. Molecular weight.

[Manufacture of finer pigments]
(Refinement pigment production example 1)
120 parts of halogenated copper phthalocyanine-based green pigment PG36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1500 parts of pulverized sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 60 ° C. And kneading for 15 hours. The mixture was poured into 5000 parts of warm water, stirred at a high-speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts refined pigment (PG-1).

(Refinement pigment production example 2)
100 parts of quinophthalone-based yellow pigment PY138 (“Pariotol Yellow K0961HD” manufactured by BASF), 3 parts of a pigment derivative (Compound 1), 800 parts of crushed salt and 180 parts of diethylene glycol are added to a 1 gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel. The mixture was kneaded at 70 ° C. for 4 hours. The mixture was added to 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts refined pigment (PY-1).

(Refinement pigment production example 3)
100 parts of a metal complex yellow pigment PY150 (LANCESS "E4GN"), 1500 parts of crushed salt and 180 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C for 6 hours. The kneaded product is poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 24 ° C. for 24 hours. It dried for time and obtained 95 parts refined pigment (PY-2).

(Fine refined pigment production example 4)
100 parts of copper phthalocyanine-based blue pigment PB15: 6 (“Lionol Blue ES” manufactured by Toyo Ink Manufacturing Co., Ltd.), 5 parts of a pigment derivative (Compound 2), 1000 parts of crushed salt, and 100 parts of diethylene glycol were added to a 1 gallon kneader made of stainless steel ( Prepared by Inoue Seisakusho) and kneaded at 50 ° C. for 12 hours. The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed with water to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts refined pigment (PB-1).

(Fine refined pigment production example 5)
300 parts of dioxazine-based purple pigment PV23 (“Rionogen Violet RL” manufactured by Toyo Ink Manufacturing Co., Ltd.) was added to 3000 parts of 96% sulfuric acid, stirred for 1 hour, and poured into 5 ° C. water. After stirring for 1 hour, it was filtered, washed with warm water until the washing solution became neutral, and dried at 70 ° C. 120 parts of the obtained acid pasting pigment, 5 parts of a pigment derivative (compound 3), 1500 parts of crushed salt and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 70 ° C. for 20 hours. did. The mixture was poured into 5000 parts of warm water, stirred at a high-speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts refined pigment (PV-1).

(Fine refined pigment production example 6)
100 parts of diketopyrrolopyrrole red pigment PR254 ("Irgafoa Red B-CF" manufactured by Ciba Specialty Chemicals), 10 parts of a pigment derivative (compound 4), 1000 parts of crushed salt, and 120 parts of diethylene glycol, 1 gallon made of stainless steel The mixture was charged into a kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 8 hours. The mixture was poured into 2000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 100 parts refined pigment (PR-1).

(Refinement Pigment Production Example 7)
100 parts of anthraquinone red pigment PR177 (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals), 5 parts of a pigment derivative (compound 5), 800 parts of crushed salt, and 180 parts of diethylene glycol, 1 gallon kneader (manufactured by Inoue Seisakusho) And kneaded at 70 ° C. for 5 hours. The mixture was poured into 4000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 100 parts refined pigment (PR-2).

[Copolymer of maleic anhydride and one or more ethylenically unsaturated monomers other than maleic anhydride (A)]
(Production example of maleic anhydride-indene copolymer (A-1))
500 parts of methyl ethyl ketone is placed in a reaction vessel equipped with a condenser and a dropping funnel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 348 parts of indene, 294 parts of maleic anhydride, and 2,2 A mixture of 10.0 parts of '-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of methyl ethyl ketone was added, and the reaction was further continued at 100 ° C. for 5 hours to obtain a weight average molecular weight. A maleic anhydride-indene copolymer solution having an (Mw) of 13,000 was obtained.

  After cooling to room temperature, about 2 g of the copolymer solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Methyl ethyl ketone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. This was added to prepare a maleic anhydride-indene copolymer (A-1) solution. In addition, it confirmed that there existed the peak of an acid anhydride group by the measurement by infrared spectroscopy.

[Manufacture of binder resin]
(Production Example 1 of Acrylic Resin (B-1))
Put 800 parts of propylene glycol monoethyl ether acetate in a reaction vessel, heat to 100 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 80.0 parts of methacrylic acid, 85.0 parts of methyl methacrylate, 85 of butyl methacrylate A mixture of 0.0 part and 10.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of propylene glycol monoethyl ether acetate was added, and the reaction was further continued at 100 ° C. for 1 hour. Thus, a solution of acrylic resin (B-1) having a weight average molecular weight (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. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether acetate was added to prepare an acrylic resin (B-1) solution.

(Production Example 2 of acrylic resin (B-2))
70.0 parts of propylene glycol monoethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, and the temperature was raised to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. Then, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.) 7.4 from the dropping tube. And a mixture of 0.4 parts of 2,2′-azobisisobutyronitrile were added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin (B-2) solution having a weight average molecular weight (Mw) of 26,000.

  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. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether acetate was added to prepare an acrylic resin (B-2) solution.

[Production of polyester dispersant]
(Production Example 1 of Polyester Dispersant 1)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 45.0 parts of methyl methacrylate, 15.0 parts of methacrylic acid, and 40.0 parts of ethyl acrylate, and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C. and dissolved in 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile is dissolved in 45.3 parts of cyclohexanone. The solution was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the weight average molecular weight was 4000. Next, 8.8 parts of Ricacid BT-100 (manufactured by Shin Nippon Rika; 1,2,3,4-butanetetracarboxylic dianhydride), 69.2 parts of cyclohexanone, and 1,8-diazabicyclo- [ 5.4.0] -7-undecene 0.2 part was added, and it was made to react at 120 degreeC for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After the reaction was completed, cyclohexanone was added so that the nonvolatile content was 50% by weight to obtain a solution of polyester dispersant-1 having an acid value of 129 mgKOH / g and a weight average molecular weight of 8,100.

(Production Example 2 of polyester dispersant)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 55.0 parts of methyl methacrylate, 5.0 parts of methacrylic acid, and 40.0 parts of ethyl acrylate, and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C. and dissolved in 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile is dissolved in 45.3 parts of cyclohexanone. The solution was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the weight average molecular weight was 4000. Next, 9.69 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries), 70.1 parts of cyclohexanone, and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst Was added and reacted at 120 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After completion of the reaction, cyclohexanone was added so that the nonvolatile content was 50% by weight to obtain a solution of polyester dispersant-2 having an acid value of 71 mgKOH / g and a weight average molecular weight of 8,100.

[Example 1]
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A green pigment dispersion 1 (DG-1) was prepared.

-1st pigment; 8.3 parts of refined pigment (PG-1)-2nd pigment; 5.4 parts of refined pigment (PY-1)-Dye derivative; 1.4 parts of compound-1-Copolymer ( A); copolymer (A-1) (nonvolatile content 20%) 27.4 parts, binder resin (B) solution; acrylic resin solution (B-1) (nonvolatile content 20%) 7.3 parts, solvent; 50.3 parts of propylene glycol monomethyl ether acetate (PGMAC)

  Next, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a green coloring composition for green color filter (CG-1).

Green pigment dispersion (DG-1) 52.0 parts Active energy ray polymerizable monomer 4.8 parts
("Aronix M-402" dipentaerythritol hexaacrylate manufactured by Toagosei Co., Ltd.)
Active energy ray polymerization initiator 2.8 parts (“Irgacure 379” 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl manufactured by Ciba Geigy ]-1-butanone)
・ Sensitizer 0.2 part (“EAB-F” 4,4′-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Co., Ltd.)
Solvent: 40.2 parts of propylene glycol monomethyl ether acetate (PGMAC)

[Examples 2 to 16, Comparative Examples 1 to 4]
Pigment, dye derivative shown in Table 1, dispersant, copolymer (A), binder resin (B), active energy ray polymerizable monomer, tertiary phosphine compound, active energy ray polymerizable initiator, sensitization The agent and the solvent were blended in the composition ratios shown in Tables 2 to 5, and a pigment dispersion and then a color filter coloring composition were obtained in the same manner as in Example 1.
However, Examples 1 to 7 are reference examples.

  Abbreviations in Tables 2 to 5 are shown below.

・ Dispersant: "byk-111"
Phosphoric acid group-containing pigment dispersant “Disperbyk111” manufactured by Big Chemie

-Copolymer (A):
"Copolymer (A-2)";"SMA2000P" (SMA base resin, maleic anhydride-styrene copolymer, copolymerization ratio 1: 2) manufactured by Sartomer Japan, dissolved in cyclohexanone, and having a nonvolatile content of 20 weight % Adjusted.

  “Copolymer (A-3)”; “SMA1000P” (SMA base resin, maleic anhydride-styrene copolymer, copolymerization ratio 1: 1) manufactured by Sartomer Japan Co., dissolved in cyclohexanone and having a nonvolatile content of 20 weight % Adjusted.

・ Comparative copolymer:
Comparative copolymer-1: “SMA1440” (SMA ester resin, maleic anhydride-styrene copolymer half ester, acid value 185 mgKOH / g) manufactured by Sartomer Japan, was dissolved in cyclohexanone to obtain a nonvolatile content of 20% by weight. It was adjusted.

-Active energy ray polymerizable monomer;
"M-402"
"Aronix M-402" dipentaerythritol hexaacrylate manufactured by Toagosei Co., Ltd.

Active energy ray polymerizable initiator:
"Irgacure 379"
“Irgacure 379” 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone manufactured by Ciba Specialty Chemicals

"Initiator-1"
Dimethylphenacylsulfonium butyltriphenylborate synthesized by the method described in JP-A-5-213861

・ Sensitizer: “EAB-F”
"EAB-F"4,4'-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Co., Ltd.

・ Solvent: “PGMAC”
Propylene glycol monomethyl ether acetate

[Dispersion stability]
About the coloring composition for color filters obtained by the Example and the comparative example, the dispersion stability was evaluated by the viscosity stability by the following method.

  Using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.), the initial viscosity of the next day after preparing the color filter coloring composition and the time-lapse viscosity accelerated at 40 ° C. for 1 week, The measurement was performed at 25 ° C. under the condition of a rotation speed of 20 rpm. From the values of the initial viscosity and the viscosity with time, the rate of change with time in viscosity was calculated by the following formula.

    [Change in viscosity with time] = | ([initial viscosity] − [viscosity with time]) / [initial viscosity] | × 100

[Evaluation of relative dielectric constant and dielectric loss tangent of coating film]
The film thickness after drying using a spin coater on a 100 mm × 100 mm, 0.7 mm thick glass substrate obtained by vapor-depositing aluminum for electrodes for the color filter coloring compositions obtained in the examples and comparative examples is 2. Coating was performed at a rotation speed of 0 μm thickness to obtain a coated substrate. Next, after drying under reduced pressure, ultraviolet exposure was performed using an ultra-high pressure mercury lamp with an integrated light amount of 300 mJ and an illuminance of 30 mW. Thereafter, the coated substrate was heated at 230 ° C. for 1 hour and allowed to cool, and then aluminum for an electrode with an area of 3.464 × 10 −4 m 2 was deposited on the obtained cured coating film, and the cured coating film was sandwiched between aluminum electrodes. A sample was made. The capacitance from 10 Hz to 1 MHz of the obtained sample was measured with an impedance analyzer (“1260 type” manufactured by Solartron) at an overprint voltage of 100 mV, and the relative dielectric constant and dielectric loss tangent value at 20 Hz were calculated. The evaluation was made according to the following criteria.

(Relative permittivity)
A: Relative dielectric constant of less than 3.0 B: Relative dielectric constant of 3.0 to less than 4.0 Δ: Relative dielectric constant of 4.0 to less than 5.0 X: Relative dielectric constant of 5.0 or more

(Dielectric loss tangent)
A: Dielectric loss tangent less than 0.02 O: Dielectric loss tangent 0.02 or more and less than 0.03 Δ: Dielectric loss tangent 0.03 or more and less than 0.04 ×: Dielectric loss tangent 0.04 or more

[Evaluation of coating adhesion and development residue]
The color composition for color filter obtained in Examples and Comparative Examples was formed with a silicon nitride film on a glass substrate (substrate 1) having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm and on the surface of a TFT liquid crystal driving substrate. On a substrate (substrate 2), a spin coater was used to apply the coating film at a rotation speed of 2.0 μm, and after drying under reduced pressure, an integrated light amount of 300 mJ was passed through a photomask using an ultrahigh pressure mercury lamp. UV exposure was performed at an illuminance of 30 mW. Thereafter, a 0.2 wt% aqueous sodium carbonate solution was used as a developer to remove the uncured portion of the coating film to form a pattern. The adhesion of this coating film and the development residue in the uncured portion were visually evaluated in three stages according to the following criteria.

(Adhesion)
◎: No pattern peeling is observed. ○: Pattern peeling is slightly observed. △: Pattern peeling is recognized.

(Development residue)
◎: No development residue in uncured part ○: Little development residue in uncured part △: Development residue in uncured part is observed

[Flatness]
The color composition for color filter obtained in Examples and Comparative Examples was formed with a silicon nitride film on a glass substrate (substrate 1) having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm and on the surface of a TFT liquid crystal driving substrate. Using a spin coater on a substrate (substrate 2), a glass film with a dried film thickness of 2.0 μm is applied to the glass substrate, and a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate. Each coating film having a thickness of 3.0 μm after drying was formed. Each coated substrate is dried under reduced pressure, exposed to ultraviolet light with an integrated light quantity of 150 mJ using an ultra-high pressure mercury lamp, heated at 230 ° C. for 1 hour, allowed to cool, and then the film thickness is increased every 2 cm diagonally from the center of the coated substrate. The film thickness uniformity was calculated by the following formula, and the flatness was evaluated.

Film thickness uniformity [%] = ((T1-T2) / T) × 100
The film thickness uniformity [%] is preferably as small as possible, and was evaluated according to the following criteria.

A: Film thickness uniformity [%] less than 4.0% B: Film thickness uniformity [%] 4.0% or more and less than 8.0% Δ: Film thickness uniformity [%] 8.0% or more 12.0 %Less than

    The above evaluation results are shown in Table 6.

  The colored compositions for color filters obtained in Examples 1 to 16 are a copolymer (A), a pigment, and a binder resin of maleic anhydride and one or more ethylenically unsaturated monomers other than maleic anhydride By using together with (B), the relative dielectric constant was small compared to those obtained in Comparative Examples 1 to 4, and the electrical characteristics were excellent.

  Especially, in Examples 7-16 used together with alkali-soluble resin (B) which has a hydroxyl group as binder resin (B), the effect that the adhesiveness of the coloring composition for color filters was more excellent was shown. In the case of using the same copolymer (A), in Examples 8 to 16, the contents of the copolymer (A) and the binder resin (B) are in the range of 5:95 to 70:30. A colored layer having excellent adhesion and no development residue could be obtained.

  In addition, Examples 10 to 16, in which a tertiary phosphine compound was added as an additive, had a lower relative dielectric constant and good results, and further, an implementation using a sulfonium organoboron complex as an active energy ray polymerizable initiator. In Examples 12 to 16, the value of the dielectric loss tangent was also small, indicating the characteristics that the electrical characteristics were more excellent.

  In addition, Examples 13 to 16 containing cyclohexyl acetate as a solvent are excellent in flatness, and on the driving substrate of the thin film transistor (TFT) type color liquid crystal display device using the color filter coloring composition of the present invention. The characteristic that it was suitable when forming a colored layer was shown.

  In addition, as a dispersant, a vinyl copolymer produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule and having two hydroxyl groups in one terminal region. Examples 5 to 16 using a polyester dispersant obtained by reacting a hydroxyl group in a polymer with an acid anhydride group in tetracarboxylic dianhydride are excellent in the stability of the coloring composition for a color filter. However, it showed the characteristic that the dielectric loss tangent is also small.

Claims (7)

Copolymer (A), pigment, binder resin (B), active energy ray polymerizable monomer, and active energy ray of maleic anhydride and one or more kinds of ethylenically unsaturated monomers other than maleic anhydride Containing a polymerization initiator, the weight ratio (A) :( B) of the copolymer (A) and the binder resin (B) is in the range of 5:95 to 70:30,
And the binder resin (B) contains the alkali-soluble resin which has a hydroxyl group, The coloring composition for color filters characterized by the above-mentioned.   The color according to claim 1, wherein the one or more types of ethylenically unsaturated monomers other than maleic anhydride are monomers selected from the group consisting of styrene, α-methylstyrene, and indene. Coloring composition for filters. The coloring composition for a color filter according to claim 1 or 2, wherein the active energy ray polymerization initiator is a sulfonium organic boron complex or an oxosulfonium organic boron complex represented by the general formula (1).
General formula (1):

(In general formula (1),
R ¹¹ is a benzyl group, an optionally substituted benzyl group, a phenacyl group, an optionally substituted phenacyl group, an aryloxy group, an optionally substituted aryloxy group, an alkenyl group Or an alkenyl group which may have a substituent,
R ¹² and R ¹³ are each independently the same as R ¹¹ or different from R ^11, and may have an alkyl group, an optionally substituted alkyl group, an aryl group, or a substituent. Good aryl group, aralkyl group, aralkyl group which may have a substituent, alkynyl group, alkynyl group which may have a substituent, alicyclic group, alicyclic group which may have a substituent, alkoxy group , An alkoxy group that may have a substituent, an alkylthio group, an alkylthio group that may have a substituent, an amino group, an amino group that may have a substituent, or R ¹² and R ¹³ may be mutually A linked ring structure,
R ¹⁴ is an oxygen atom or a lone pair,
X ⁻ is any anion. ) Furthermore, cyclohexyl acetate is contained as a solvent , The coloring composition for color filters in any one of Claims 1-3 characterized by the above-mentioned. Furthermore, as a dispersant,
Hydroxyl group in a vinyl copolymer produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule, and having two hydroxyl groups at one end region The coloring composition for color filters according to any one of claims 1 to 4, comprising a polyester dispersant obtained by reacting an acid anhydride group in tetracarboxylic dianhydride.   A color filter comprising a filter segment formed using the color filter coloring composition according to claim 1. A filter segment having a colored layer formed on a driving substrate of a thin film transistor (TFT) color liquid crystal display device using the colored composition for a color filter according to any one of claims 1 to 5. Characteristic color filter.