JP2019113751A - Method of producing color filter coloring composition and colored curable composition - Google Patents

Abstract

To provide a method of producing a color filter coloring composition which offers good viscosity stability, a high contrast ratio and high brightness and, when used as a colored curable composition, exhibits high solvent resistance, good developability, and high coloring power, and to provide a method of producing the colored curable composition.SOLUTION: The above challenge is cleared by a method of producing a color filter coloring composition, the method comprising adding at least one type of green pigment and at least one type of yellow pigment together such that a total of three or more types of green and yellow pigments are added, and co-dispersing the pigments using a disperser.SELECTED DRAWING: None

Description

  The present invention relates to a colored composition used to manufacture a color filter used in a liquid crystal display device, a solid-state imaging device or the like, and a method of manufacturing a colored curable composition.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the degree of polarization of light passing through the first polarizing plate to control the amount of light passing through the second polarizing plate. Is a display device that performs display, and the type using a twisted nematic (TN) liquid crystal is mainstream. The liquid crystal display device enables color display by providing a color filter between two polarizing plates, and has recently been used in televisions and personal computer monitors etc. There is a growing demand for high color reproducibility.

  A color filter is a transparent substrate such as glass on which two or more fine band (stripe) filter segments of different hues are arranged in parallel or crossing, or a fine filter segment arrayed in a fixed length and width direction It consists of what was arranged in. Generally formed of red, green, and blue three-color filter segments, and each segment is as fine as several microns to several hundred microns, and is regularly arranged in a predetermined arrangement for each hue .

  Generally, in a color liquid crystal display device, a transparent electrode for driving the liquid crystal is formed on the color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. There is. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof needs to be carried out generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, a method called a pigment dispersion method in which a pigment having excellent heat resistance and light resistance is used as a colorant is mainly used as a method for producing a color filter.

  In the production of green filters, it is common to use various phthalocyanine-based compounds as colorants, and many proposals have been made for compositions for color filters containing these.

  Patent Document 1 discloses a coloring composition for a color filter containing a coloring agent, a binder resin, and an organic solvent, wherein the coloring agent is an aluminum phthalocyanine pigment represented by the general formula (2A) or the general formula (2B). And a pigment having an acid group content of 100 to 600 μmol / g have been proposed.

  However, since these coloring compositions for color filters are used by dispersing and mixing pigments one by one, not only the viscosity stability is deteriorated when mixed, but also optical characteristics such as contrast ratio and lightness In some cases, solvent resistance and poor developability may be caused when forming a colored curable composition, and further improvement is desired.

JP 2012-247588 A

  The object of the present invention is that the viscosity stability of the coloring composition is good, the contrast ratio and the lightness are high, the solvent resistance is high when it is made a colored curable composition, the developability is good and the coloring power is high. It is an object of the present invention to provide a coloring composition for a color filter, and a method for producing a coloring curable composition.

  As a result of intensive studies, the present inventors combinedly use at least one or more types of green pigments and at least one or more types of yellow pigments such that the total of the types of green and yellow pigments is three or more. It discovered that the said subject was solvable by adding and co-dispersing using a dispersing machine, and came to this invention.

  That is, in the present invention, at least one or more types of green pigments and at least one or more types of yellow pigments are used in combination so that the total of the types of green pigments and yellow pigments is 3 or more, and a dispersing machine is used. The present invention relates to a method for producing a coloring composition for a color filter according to claim 1, characterized by co-dispersion.

  Further, the present invention relates to the method for producing a coloring composition for color filter, which further comprises co-dispersing a basic dispersant, an acidic dispersant and a binder resin.

  The present invention also relates to a method for producing a colored curable composition for color filter, which further comprises adding a polymerizable monomer to the colored curable composition for color filter produced by the above-mentioned production method.

  According to the present invention, the viscosity stability of the coloring composition is good, the contrast ratio and the lightness are high, the solvent resistance is high when it is made a colored curable composition, the developability is good and the coloring power is high. The coloring composition for color filters and the coloring curable composition can be manufactured.

Hereinafter, the present invention will be described in detail.
In the present application, “(meth) acryloyl”, “(meth) acrylic”, “(meth) acrylic acid”, “(meth) acrylate” or “(meth) acrylamide” are particularly described. Unless there is any, respectively, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide" It shall represent.
In addition, “CI” listed in the present specification means a color index (CI).

  The present invention is a color filter characterized in that at least one or more types of green pigments and at least one or more types of yellow pigments are used in combination such that the total of the types of green and yellow pigments is three or more. It is a manufacturing method of a coloring composition.

(Green pigment)
Examples of the green pigment used in the present invention include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 62, 63, Zinc phthalocyanine pigments described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-70342, etc., and aluminum phthalocyanine pigments described in JP-B-4893859 etc. can be mentioned. In particular, from the viewpoint of contrast ratio, brightness and viscosity stability of the filter segment, C.I. I. Pigment greens 58, 62, 63 are preferred. These green pigments may be used alone or in combination of two or more depending on the desired color characteristics.

(Yellow pigment)
As a yellow pigment used in the present invention, 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, 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, 181, 181, 181, 181, Yellow pigments such as 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 218, 219, 220, 221, 231 can be used. In particular, from the viewpoint of the contrast ratio of the filter segment and the lightness, I. Pigment yellow 138, 150 and 231 are preferred. These yellow pigments can be used alone or in combination of two or more depending on the desired color characteristics.

  The production method of the present invention is characterized in that at least one or more types of green pigments and at least one or more types of yellow pigments are added in combination such that the total of the types of green pigments and yellow pigments is three or more. Do. By combining and adding so that the total of the kind of a green pigment and a yellow pigment will be 3 or more types, it is excellent in the viscosity stability at the time of setting it as a coloring composition, contrast ratio and lightness are high, and it was set as the coloring curable composition. Solvent resistance, developability and coloring power at the time of improvement.

  Preferred as a combination of a green pigment and a yellow pigment is C.I. I. Pigment green 58 / C. I. Pigment green 62 / C. I. Pigment yellow 138 / C. I. Pigment yellow 231. Among them, C.I. I. Pigment green 58 / C. I. Pigment yellow 138 / C. I. Pigment yellow 231 is more preferable.

  The mixing ratio of the green pigment and the yellow pigment is preferably in the range of 10/90 to 90/10, more preferably in the range of 20/80 to 80/20, and preferably 30/70 to 70. The range of / 30 is more preferable. By setting the mixing ratio of the green pigment and the yellow pigment to the above range, the contrast ratio and the lightness are high, and the viscosity stability is favorable, which is preferable.

(Covariance)
As a method for producing a coloring composition and a coloring curable composition according to the present invention, at least one or more green pigments and at least one or more yellow pigments are used, and the total of the types of green pigments and yellow pigments is three or more. It is preferable to carry out co-dispersion using a dispersing machine so as to obtain Co-dispersion in the present invention refers to mixing three or more pigments and performing dispersion processing under the same conditions. By co-dispersion, the fine pigment particles can be finely divided and dispersed, and a color composition for color filter having excellent viscosity stability after dispersion can be produced.

  The method of co-dispersion is, for example, a kneader, a 2-roll mill, and a mixture obtained by pre-mixing at least three pigments together with a resin-type dispersant, a binder resin and an organic solvent described later and using a homogenizer or the like. It can be carried out by dispersing with various dispersing means such as a 3-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. Among them, co-dispersion using a media type wet disperser is preferable.

By combining and adding at least one or more types of green pigments and at least one or more types of yellow pigments such that the total of the types of green and yellow pigments is three or more, a good colored composition or a colored cured product can be obtained. Although the reason why the sex composition can be produced is not clear, the inventor thinks as follows.
Since the equilibrium state of resin adsorption when mixed with the equilibrium state of resin adsorption when each coloring composition is dispersed alone is different, it is assumed that a new equilibrium state is taken. At this time, movement of the resin occurs, and it is assumed that the pigments from which the resin is detached are aggregated and the viscosity stability is deteriorated. On the other hand, when co-dispersion, the adsorption state of the resin is maintained at an optimum state, so it is assumed that the viscosity stability is good.

(Basic dispersant)
In the present invention, it is preferable to add a basic dispersant and an acidic dispersant as a resin type dispersant. The resin type dispersant has a pigment affinity site having a property of adsorbing to the added pigment, and a site compatible with the pigment carrier, and adsorbs to the additive pigment to stabilize the dispersion to the pigment carrier It works. Specific examples of the resin type dispersant include polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt , Polysiloxanes, long chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, amides formed by the reaction of these modified products, poly (lower alkyleneimine) with polyesters having free carboxy groups, and salts thereof Etc., (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester, modified polya Relate system, an ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, is not necessarily limited thereto.

<Basic Dispersant>
As the basic dispersant used in the present invention, a polymer dispersant having a basic functional group is preferable, and a nitrogen atom-containing graft copolymer, a tertiary amino group in a side chain, a quaternary ammonium base, a nitrogen-containing complex, A nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing a ring and the like are preferable. The basic dispersant is preferably used in an amount of about 5 to 200% by mass, and more preferably about 10 to 100% by mass, from the viewpoint of film formation.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2070, 2095, 2150, 2155, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P 104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen et al., SOLSPERSE-3000, 9000, manufactured by Japan Lubrizol Corporation. 3000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 20000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32500, 32500, 34750, 35100, 36600, 38500, 41000, 41090, 41090, 41090 53095, 55000, 56000, 76500, etc., BASF EFKA-46, 47, 48, 452, 458, 4008, 4009, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403 , 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 453, 454, 4550, 4550, 4560, 4 00,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of Ajisupa -PA111, PB711, PB821, PB822, PB824, and the like are preferable.

<Acidic dispersant>
As an acidic dispersing agent used by this invention, it is preferable to contain following (S1) or (S2) as an acidic dispersing agent which has a carboxy group.
(S1) An acidic dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride.
(S2) a weight obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride An acidic dispersant that is a combination.

[Acid Dispersant (S1)]
The acidic dispersant (S1) can be produced by a known method such as WO 2008/007776, JP 2008-029901, JP 2009-155406 and the like. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at an end, and for example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Among them, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used because the terminal hydroxyl group is preferably plural.

  That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, has a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) obtained by polymerizing the ethylenically unsaturated monomer (r) contained. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride to form an ester bond, while the anhydride ring is opened to form a carboxylic acid. Produces

[Acid Dispersant (S2)]
The acidic dispersant (S2) can be produced by a known method such as JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, and, for example, a compound having a hydroxyl group ( Obtained by polymerizing the ethylenically unsaturated monomer (r) in the presence of the reaction product of the hydroxyl group of q) with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride Be Among them, in the presence of a reaction product of a hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride Preferably, it is a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1).

  (S1) and (S2) are differences in whether the introduction of the polymer portion obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. Although molecular weight etc. may differ somewhat depending on various conditions, if the raw material and the reaction conditions are the same, theoretically the same one can be obtained.

  As a preferable addition amount of a resin type dispersing agent, 10-50 mass parts is preferable with respect to 100 mass parts of pigments. Moreover, as a mixing ratio of a basic dispersing agent and an acidic dispersing agent, 20 / 80-80 / 20 of a basic dispersing agent / acidic dispersing agent is preferable at the mass ratio of solid content. By setting the amount of addition of the resin-type dispersant in the above range, it is possible to produce a colored composition excellent in viscosity stability.

<Binder resin>
In the present invention, a binder resin is preferably added. The binder resin means a resin other than the above-mentioned resin type dispersant. What disperse | distributes a pigment, or makes it dye and permeate | transmit, Comprising: A conventionally well-known thermoplastic resin, a thermosetting resin, etc. are mentioned. The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light range.

  As a preferable addition amount of binder resin, 10-50 mass parts is preferable with respect to 100 mass parts of pigments. By making the addition amount of binder resin into the said range, the coloring composition excellent in viscosity stability can be manufactured.

  As a thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin And polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

In the case of using in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenic unsaturated monomer. Furthermore, in order to further improve the photosensitivity, an active energy ray curable resin having an ethylenically unsaturated double bond can also be used.
In particular, when an active energy ray-curable resin having an ethylenically unsaturated double bond in a side chain is used as the alkali-developable colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the pigment and the pigment derivative are fixed, the heat resistance is improved, and it is possible to suppress the color fading (brightness reduction) due to the heat of the pigment and the pigment derivative. In addition, it also has the effect of suppressing aggregation and precipitation of the pigment and the dye derivative in the development step.

  Examples of the alkali-soluble resin obtained by copolymerizing the acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxy group and a sulfo group. Specifically as the alkali-soluble resin, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or An isobutylene / (anhydride) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, in particular an acrylic resin having an acidic group, is preferably used because it is high in heat resistance and transparency.

  As an energy ray curable resin having an ethylenically unsaturated active double bond, a polymer having a reactive substituent such as a hydroxy group, a carboxy group, an amino group or the like is reacted with an isocyanate group, an aldehyde group, an epoxy group or the like A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a substituent or a cinnamic acid is used. In addition, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is a half ester by a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. It is also possible to use

  As a thermoplastic resin, one having both alkali solubility and energy ray curing performance is also preferable as a coloring composition for a color filter.

  The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypoly (Meth) acrylates such as thylene glycol (meth) acrylate, or (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, dye Acetone (meth) acrylamide or (meth) acrylamides such as acryloyl morpholine, styrene, or styrenes such as α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether Vinyl ethers, vinyl acetate, or fatty acid vinyls such as vinyl propionate can be mentioned.

  Or cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimidodiphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4 Phenylenedimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-sk N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzoimidazolyl) phenyl N-substituted maleimides such as maleimide, 9-maleimidacridine and the like.

  Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin modified maleic resin, rosin modified fumaric resin, melamine resin, urea resin, and phenol resin. Among them, epoxy resin and melamine resin are more preferably used from the viewpoint of heat resistance improvement.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000, in order to disperse the pigment preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  The weight-average molecular weight (Mw) and number-average molecular weight (Mn) used herein are HLC-8220GPC (manufactured by Tosoh Corp.) as an apparatus, and TSK-GEL SUPER HZM-N is used as a column connected in twos as a column, It is a polystyrene conversion molecular weight measured using THF as.

  When a binder resin is used as a coloring composition for a color filter, it is preferable to use a pigment adsorbing group and a carboxy group acting as an alkali-soluble group during development, and an aliphatic group and an aromatic group acting as an affinity group for a pigment carrier and a solvent. The balance is important for pigment dispersibility, permeability, developability, and durability, and it is preferred to use a resin having an acid value of 20 to 300 mg KOH / g. By making an acid value into the said range, the solubility to a developing solution can manufacture favorable colored composition and colored curable composition.

  The binder resin is preferably used in an amount of 10 to 500 parts by mass with respect to 100 parts by mass of the pigment. By making the addition amount of binder resin into the said range, solvent resistance and coloring ability can manufacture the coloring composition and coloring curable composition favorable.

(Dye derivative)
In the receiving composition obtained by the production method of the present invention, phthalimidomethyl which may have a basic substituent, an acidic substituent or a substituent as an organic pigment, anthraquinone, acridone or triazine as a dye derivative It can include compounds in which a group is introduced. As such a dye derivative, for example, JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469. JP-A 2001-335717, JP-A 2003-128669, JP-A 2004-091497, JP-A 2007-156395, JP-A 2008-09873, JP-A 2008-094986, and the like. Those described in JP2008-095007A, JP2008-195916A, JP-B-4585781 and the like can be used, and these can be used alone or as a mixture of two or more.

<Organic solvent>
In the present invention, the pigment is sufficiently dispersed and infiltrated into the pigment carrier, and it is easily applied on a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a filter segment. To contain organic solvents. The organic solvent is selected in consideration of the solubility of each component of the coloring composition as well as the safety, as well as the application property of the coloring composition is good.

As the organic solvent, for example, ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 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, 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, 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 glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin alcohol, tripropylene, 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, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents may be used alone or in combination of two or more at an arbitrary ratio as needed.

  Among these, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, among others, because of good pigment dispersibility, permeability and coatability of coloring composition. It is preferable to use glycol acetates such as acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the pigment because it can adjust the coloring composition to an appropriate viscosity and form a filter segment having an intended uniform film thickness. preferable.

<Polymerizable monomer>
It is preferable to add a polymerizable monomer to the colored composition obtained by the production method of the present invention. The polymerizable monomer includes a monomer or an oligomer which is cured by ultraviolet light or heat to form a transparent resin. The presence of the monomer or oligomer in the vicinity of the pigment is considered to increase the solvent resistance when the pigment is coated and protected to form a colored curable composition.

Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglyci Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Various acrylic and methacrylic esters such as (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy ester Examples include, but not limited to, chill (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These polymerizable compounds can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The compounding amount of the polymerizable monomer is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the pigment, and more preferably 10 to 300 parts by mass from the viewpoint of photocurability and developability.

<Photoinitiator>
In the colored composition of the present invention, a photopolymerization initiator is added to cure the composition by ultraviolet irradiation and to form a filter segment by a photolithographic method, and a solvent developable or alkali developable colored curable composition It can be prepared in the form of

As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dil dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Thioxanthone compounds of the formula: 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphen) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -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- Triazine compounds such as (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenyl phosphine oxide or 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphor quinone, ethyl anthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound etc. are used.
These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as needed.

  Among these, in order to produce a color filter having good pattern shape and linearity, it is preferable to include an acetophenone compound or an oxime ester compound as a photopolymerization initiator.

  The oxime ester compound absorbs ultraviolet light to cause cleavage of the N-O bond of the oxime to generate iminyl radical and benzoyloxy radical. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small exposure amount. As an oxime ester photopolymerization initiator, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), 1,2-, Octadione-1- [4- (phenylthio)-, 2- (O-benzoyloxime)] is preferred.

  The acetophenone compound is cleaved to generate a radical having an amino group to be an active hydrogen donor, which can reduce the effect of oxygen inhibition which becomes a problem in UV curing, and can cure the surface of the coating film. . As an acetophenone compound, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-, which is an α-aminoalkylacetophenone compound 1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone is preferred.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment, and more preferably 3 to 150 parts by mass from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
As sensitizers, unsaturated ketones represented by chalcone derivatives, dibenzalacetone etc., 1,2-diketone derivatives represented by benzyl and camphorquinone etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyrin derivative, anurene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acyl phosphine oxide, methylphenyl glyoxylate, benzyl, 9, 10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, or 4,4′-tetra (t-butylperoxycarbonyl) benzopheno And 4,4'-diethylaminobenzophenone and the like.
These sensitizers can be used alone or in combination of two or more at an arbitrary ratio as required.

  More specifically, edited by Ogawara Shin et al., "Dye Handbook" (1986, Kodansha), edited by Ogawara Shin et al., "Chemicals of functional dyes" (1981, CMC), edited by Ikemori Tadajiro et al. Specific examples thereof include, but are not limited to, the sensitizers described in “Specially functional materials” (1986, CMC). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator contained in the coloring composition, and 5 to 50 parts from the viewpoint of photocurability and developability. It is more preferable that it is a part.

<Antioxidant>
The coloring composition for color filters of the present invention can contain an antioxidant. In order to prevent the photopolymerization initiator and the thermosetting compound contained in the coloring composition for color filter from being oxidized and yellowed due to a heat process at the time of heat curing or ITO annealing, the antioxidant is the transmittance of the coating film. Can be raised. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation in the heating step and to obtain a high transmittance of the coating film.

  The "antioxidant" in the present invention may be a compound having an ultraviolet light absorbing function, a radical trapping function, or a peroxide decomposing function, and specifically, a hindered phenol type or hindered amine type as an antioxidant. Examples thereof include phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylate and triazine compounds, and known ultraviolet light absorbers, antioxidants and the like can be used.

  Among these antioxidants, preferred are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants from the viewpoint of achieving both the transmittance and sensitivity of the coating film. Agents. Also, more preferably, hindered phenol antioxidants, hindered amine antioxidants, or phosphorus antioxidants are used.

  Examples of hindered phenolic antioxidants include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -Tert-Butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-4 Nonylphenol, 2,2'-Isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-Butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- S- (6-t-Butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'-thiodiethyl bis- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-Tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydro) And the like. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

  As the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butane tetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-Tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-Pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomeric types having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  As a phosphorus antioxidant, tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 'isopropylidene diphenol alkyl phosphite, tris nonyl phenyl phosphite, tris dinonyl phenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-Di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidene bis (3-methyl-) 6-t-Butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxy phosphonyloxy)-Ben Zen, ethyl phosphite bis (2,4-di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As a sulfur-based antioxidant, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, etc. may be mentioned. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, compounds of oligomer type and polymer type having a benzotriazole structure can be used.

  Specific examples of benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, and 2-hydroxybenzophenone. Hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2- Examples thereof include hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  As a triazine type antioxidant, a 2, 4- bis (allyl) 6- (2-hydroxyphenyl) 1, 3, 5- triazine etc. are mentioned. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

  Examples of the salicylate-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate and the like. In addition, oligomer type and polymer type compounds having a salicylate structure can also be used.

  These antioxidants can be used alone or in combination of two or more at an arbitrary ratio as required.

  The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on the mass of the solid content of the color composition for color filter, because the lightness and sensitivity are good.

<Amine compounds>
In addition, the coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen.

  As such an amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethyl paratoluidine etc. are mentioned.

<Leveling agent>
It is preferable to add a leveling agent to the colored composition of the present invention in order to improve the leveling properties of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. 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 Japan, and the like. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie Japan. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by mass based on the total mass of the coloring composition (100% by mass).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when it is added to a coloring composition, It is characterized by low surface tension reduction ability, and in addition to low surface tension reduction ability, it is useful that the wettability to the glass plate is good, and the addition amount at which defects of the coating film due to foaming do not appear. Those which can sufficiently suppress the chargeability can be preferably used. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2203. -2-207, but not limited thereto.

  The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more. Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene 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 stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines; and fluorine-based and silicone-based surfactants.

<Hardening agent, hardening accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening agent, the hardening accelerator, etc. as needed. As a curing agent, a phenolic resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound and the like are effective, but not particularly limited thereto, a thermosetting resin Any curing agent may be used as long as it can react with it. Among these, a compound having two or more phenolic hydroxyl groups in one molecule, and an amine curing agent are preferably mentioned. 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- Tyl-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, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

<Other additive components>
The coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity over time. Further, in order to enhance the adhesion to the transparent substrate, an adhesion improver such as a silane coupling agent may be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl phosphine, etc. Organic phosphine, phosphite and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the pigment.

  Adhesion improvers include vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,3, 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 (amino Ethyl) γ-aminopropyl trie Xysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the pigment in the coloring composition.

<Mixing of coloring composition and various additives>
As a method of mixing a coloring composition and an additive such as an antioxidant or a leveling agent to produce a colored curable composition, stirring and mixing with a disper or the like, shear mixing with a homogenizer or the like, a media type wet dispersing machine or the like Dispersion mixing can be used. By uniformly mixing the coloring composition and the other components, a colored curable composition having good developability can be produced.

<Removal of coarse particles>
The colored composition and the colored curable composition of the present invention may be coarse particles of 5 μm or more, preferably 1 μm or more, and more preferably 0.2 μm or more by means of centrifugation, filtration with a sintered filter or membrane filter. It is preferable to remove coarse particles of 5 μm or more and mixed dust. Thus, the coloring composition preferably contains substantially no particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, color filters used in the present invention will be described.
The color filter used in the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, and the green filter segment is formed from the colored composition or the colored curable composition of the present invention. It will be Also, the color filter may further include a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment.

  The red filter segment can be formed using a conventional red coloring composition comprising a red pigment and a pigment carrier. Examples of red coloring compositions 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, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 255, 264, 270, 272, 273, 274, 277, 278, 279, Mention may be made of red pigments such as 280, 281, 282, 283, 284, 285, 286 or 287. In addition, red dyes such as xanthene dyes, azo dyes, disazo dyes, and anthraquinone dyes can also be used. Specifically, C.I. I. Salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289, 338 and the like can be mentioned.

  In addition, C.I. I. Orange pigments such as C.I. pigment orange 43, 71 or 73, 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, 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, 181, 181, 181, 181, 82,185,187,188,193,194,196.198,199,213,214,218,219,220,221 or may be used in combination of a yellow pigment 231, and the like. In addition, orange dyes and / or yellow dyes such as quinoline dyes, azo dyes, disazo dyes, and methine dyes can also be used.

  The blue filter segment can be formed using a conventional blue coloring composition comprising a blue pigment and a pigment carrier. Examples of blue pigments include C.I. I. Pigment blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. In addition, a violet pigment can be used in combination with the blue coloring composition. As a purple pigment which can be used in combination, C.I. I. And violet pigments such as CI pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like. In addition, it is also possible to use a salt forming compound of a basic dye or an acid dye exhibiting a blue or purple color. When a dye is used, triarylmethane dyes or xanthene dyes are preferred in terms of lightness.

<Method of manufacturing color filter>
The color filter used in the present invention can be produced by a printing method or a photolithography method.

  Since formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as printing ink, it is excellent in mass productivity at low cost as a method of manufacturing a color filter. Furthermore, with the development of printing technology, printing of fine patterns with high dimensional accuracy and smoothness can be performed. In order to print, it is preferable to set it as a composition which an ink does not dry and solidify on the printing plate or on a blanket. In addition, it is important to control the flowability of the ink on the printing press, and the viscosity of the ink can be adjusted by a dispersant or an extender pigment.

  When a filter segment is formed by photolithography, the coloring composition prepared as the above-mentioned solvent development type or alkali development type coloring resist material is coated on a transparent substrate by spray coating, spin coating, slit coating, roll coating, etc. The dry film is applied to a thickness of 0.2 to 5 μm by a method. The film dried if necessary is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, the uncured area is removed by immersion in a solvent or an alkaline developer or by spraying the developer to remove a non-cured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate | stimulate superposition | polymerization of a coloring resist material, heating can also be given as needed. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above-mentioned printing method.

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

  The color filter used in the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method, etc. in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. . In the transfer method, filter segments are formed in advance on the surface of a peelable transfer base sheet, and the filter segments are transferred to a desired substrate.

  Before forming the color filter segments on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, although a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, it is not limited thereto. Alternatively, thin film transistors (TFTs) may be formed in advance on the above-described transparent substrate or reflective substrate, and then the color filter segments may be formed. Moreover, an overcoat film, a transparent conductive film, etc. are formed on the color filter of this invention as needed.

  The color filter is bonded to the opposing substrate using a sealing agent, and liquid crystal is injected from the injection port provided in the seal portion, and then the injection port is sealed, and a polarizing film or retardation film is formed on the outside of the substrate as necessary. By bonding, a liquid crystal display panel is manufactured.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), critical alignment (VA), and optically convensend bend (OCB). Etc. can be used in a liquid crystal display mode in which coloring is performed using a color filter.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereby. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively. Also, "PGMAc" means propylene glycol monomethyl ether acetate.

  The weight-average molecular weight (Mw) and number-average molecular weight (Mn) used herein are HLC-8220GPC (manufactured by Tosoh Corp.) as an apparatus, and TSK-GEL SUPER HZM-N is used as a column connected in twos as a column, It is a polystyrene conversion molecular weight measured using THF as. The solid content of the resin is the value of the solid content measurement obtained from the loss on drying when 0.5 g of the resin solution is precisely weighed and placed in a 180 ° C. dryer for 20 minutes.

<Method of producing acidic dispersant>
(Production Example 1)
(Acidic dispersant P1)
10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate and 50 parts of propylene glycol monomethyl ether acetate are charged into a reaction vessel equipped with a gas introducing pipe, temperature, condenser and stirrer. Replaced by
The inside of the reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and a reaction was conducted for 7 hours while adding a solution of 0.1 part of 2,2'-azobisisobutyro nitrile to 90 parts of propylene glycol monomethyl ether acetate. Solid content measurement confirmed that 95% had reacted.
19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone, 0.4 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst, and added at 100 ° C. It was allowed to react for 7 hours. It is confirmed that acidity of 98% or more is half-esterified by measurement of acid value, and the reaction is ended, and propylene glycol monomethyl ether acetate is added to dilute so that solid content becomes 40%, and acid An acidic dispersant P1 having a weight of 77 mg KOH / g and a weight average molecular weight of 8500 was obtained.

(Production Examples 2 and 3)
(Acid dispersants P2 and P3)
The synthesis was carried out in the same manner as in Production Example 1 except that the raw materials and charging amounts described in Table 1 were used, to obtain acidic dispersants P2 and P3.

The abbreviations in Table 1 mean the following:
AIBN: 2,2'-azobisisobutyronitrile DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene PGMAc: propylene glycol monomethyl ether acetate

<Method of producing basic dispersant>
(Basic dispersant Q1)
In a four-neck separable flask equipped with a thermometer, stirrer, distillation tube and condenser, 70 parts of methyl ethyl ketone, 96.1 parts of n-butyl acrylate, 2.8 parts of spartein, 1.9 parts of ethyl bromoisobutyrate are charged The temperature was raised to 40 ° C. under a nitrogen stream. After charging 1.1 parts of cuprous chloride, the temperature was raised to 75 ° C. to initiate polymerization. After 3 hours of polymerization, the polymerization solution is sampled to confirm that the polymerization yield is 95% or more from the solid content of polymerization, and 3.9 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of methyl ethyl ketone are added. And further polymerization. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the obtained resin solution is diluted with 100 parts of methyl ethyl ketone, 60 parts of a cation exchange resin "Diion PK228LH (manufactured by Mitsubishi Chemical Co., Ltd.)" is added, and the mixture is stirred at room temperature for 1 hour. A portion of Kyoward 500 SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and stirring was performed for 30 minutes. The residue of the polymerization catalyst was removed by removing the cation exchange resin and the adsorbent by filtration. Furthermore, the resin solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a solution of a basic dispersant Q1 (Mn = 10200, Mw = 12200, amine value 14 mg KOH / g) having a nonvolatile content of 40% by mass.

(Basic dispersant Q2)
In a four-neck separable flask equipped with a thermometer, stirrer, distillation tube and condenser, 70 parts of methyl ethyl ketone, 88.0 parts of n-butyl acrylate, 2.8 parts of spartein and 1.9 parts of ethyl bromoisobutyrate are charged The temperature was raised to 40 ° C. under a nitrogen stream. After charging 1.1 parts of cuprous chloride, the temperature was raised to 75 ° C. to initiate polymerization. After 3 hours of polymerization, the polymerization solution is sampled to confirm that the polymerization yield is 95% or more from the solid content of polymerization, and 12.0 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of methyl ethyl ketone are added. And further polymerization. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the obtained resin solution is diluted with 100 parts of methyl ethyl ketone, 60 parts of a cation exchange resin "Diion PK228LH (manufactured by Mitsubishi Chemical Co., Ltd.)" is added, and the mixture is stirred at room temperature for 1 hour. A portion of Kyoward 500 SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and stirring was performed for 30 minutes. The residue of the polymerization catalyst was removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a solution of basic dispersant Q2 (Mn = 11200, Mw = 14200, amine value 43 mg KOH / g) having a nonvolatile content of 40% by mass.

(Basic dispersant Q3)
In a four-neck separable flask equipped with a thermometer, stirrer, distillation tube and condenser, 70 parts of methyl ethyl ketone, 76.0 parts of n-butyl acrylate, 2.8 parts of spartein, 1.9 parts of ethyl bromoisobutyrate are charged The temperature was raised to 40 ° C. under a nitrogen stream. After charging 1.1 parts of cuprous chloride, the temperature was raised to 75 ° C. to initiate polymerization. After 3 hours of polymerization, the polymerization solution is sampled to confirm that the polymerization yield is 95% or more from the solid content of polymerization, and 24.0 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of methyl ethyl ketone are added. And further polymerization. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the obtained resin solution is diluted with 100 parts of methyl ethyl ketone, 60 parts of a cation exchange resin "Diion PK228LH (manufactured by Mitsubishi Chemical Co., Ltd.)" is added, and the mixture is stirred at room temperature for 1 hour. A portion of Kyoward 500 SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and stirring was performed for 30 minutes. The residue of the polymerization catalyst was removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a solution of basic dispersant Q3 (Mn = 10210, Mw = 11400, amine value 86 mg KOH / g) having a nonvolatile content of 40% by mass.

<Method of producing binder resin solution>
(Preparation of Acrylic Resin Solution 1)
196 parts of cyclohexanone is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer are attached to a separable four-necked flask, the temperature is raised to 80 ° C., and the inside of the reaction vessel is purged with nitrogen and then dropped. From tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumyl phenol ethylene oxide modified acrylate ("Alonix M110" manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1 part and 1.1 parts 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 a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and propylene glycol monomethyl is obtained so that non-volatile content is 20% by mass in the resin solution synthesized above. Ether acetate was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

<Method of producing pigment>
(Production of Hydroxy Aluminum Phthalocyanine 1)
In a reaction vessel, 225 parts of phthalonitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this was added 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water under stirring to obtain a green slurry. The slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. while stirring at 40 ° C. for 3 hours. The green precipitate was filtered, washed with water, and dried to obtain 102 parts of hydroxyaluminum phthalocyanine 1 represented by the following formula (101).

(Production of green pigment (PG-1))
In a reaction vessel, 100 parts of hydroxyaluminum phthalocyanine 1 represented by the formula (101) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product is filtered, washed with methanol and dried to obtain 114 parts of an aluminum phthalocyanine pigment represented by the following formula (102).
Subsequently, solvent salt milling was performed. 100 parts of the aluminum phthalocyanine pigment represented by the formula (102), 1200 parts of sodium chloride, and 240 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70 ° C. for 6 hours. The kneaded product is poured into 3000 parts of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and dried at 80 ° C. overnight. 98 parts of pigment (PG-1) were obtained. The average primary particle size was 35.6 nm.

(Production of green pigment (PG-2))
In a reaction vessel, 100 parts of hydroxyaluminum phthalocyanine 1 represented by the formula (101) and 43.2 parts of diphenylphosphinic acid were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol and dried to obtain 112 parts of an aluminum phthalocyanine pigment represented by the following formula (103). The obtained aluminum phthalocyanine pigment represented by Formula (103) was subjected to the same solvent salt milling method as the green pigment (PG-1) to obtain a green pigment (PG-2). The average primary particle size was 29.5 nm.

(Production of yellow pigment (PY-1))
C. I. 100 parts of CI Pigment Yellow 138 (BASF trade name, PARIOTOL Yellow K0961 HD), 1200 parts of sodium chloride, and 240 parts of diethylene glycol are charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70 ° C for 6 hours Salt milling was performed. The kneaded product is poured into 3000 parts of hot water, stirred at 70 ° C. for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. A pigment (PY-1) was obtained. The average primary particle size was 28.7 nm.

(Production of yellow pigment (PY-2))
To 100 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 110 parts of 2,3-naphthalenedicarboxylic acid anhydride and 154 parts of benzoic acid are added, heated to 180 ° C., and stirred for 6 hours while distilling off water. went. After cooling to room temperature, the reaction mixture was poured into 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, 900 parts of water and 150 parts of potassium hydroxide were added to the above product, and the mixture was heated to 90 ° C. and stirred for 16 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, the above product was added to 300 parts of methyl benzoate, 73 parts of tetrachlorophthalic anhydride and 123 parts of benzoic acid were further added, and the mixture was heated to 180 ° C. and stirred for 5 hours while distilling off water. After cooling to room temperature, the reaction mixture was poured into 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. As a result of mass spectrometry by TOF-MS, it was identified as the following formula (201).
Subsequently, solvent salt milling was performed. C.I. used for the yellow pigment (PY-1). I. A yellow pigment (PY-2) was obtained in the same manner as the yellow pigment (PY-1) except that the pigment yellow 138 was changed to the following formula (201). The average primary particle size was 29.5 nm.

(Production of yellow pigment (PY-3))
C.I. used for the yellow pigment (PY-1). I. Pigment yellow 138, C.I. I. Solvent salt milling was performed in the same manner as for the yellow pigment (PY-1) except that the pigment yellow 150 was changed to trade name E4GN manufactured by LANXESS, to obtain a yellow pigment (PY-3). The average primary particle size was 25.5 nm.

Example 1
(Preparation of Colored Composition 1)
After stirring and mixing the mixture of the following composition so as to be uniform, using Eiger Mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) as a media type wet disperser using zirconia beads with a diameter of 0.5 mm After dispersing for 4 hours, the solution was filtered through a filter with a pore size of 5 μm to prepare a coloring composition 1.
DIC Corporation C.I. I. Pigment green 58 (Fast Gen Green A 350)
6.0 parts Yellow pigment (PY-1) 9.8 parts Yellow pigment (PY-2) 4.2 parts Acidic dispersant P1 12.5 parts Basic dispersant Q1 10.0 parts Acrylic resin solution 1 21.5 102.9 parts of organic solvent (PGMAc)

[Examples 2 to 25]
(Preparation of Colored Compositions 2 to 25)
Colored compositions 2 to 25 were produced in the same manner as in Example 1 except that the amounts of pigment and dispersant added were changed as shown in Table 2.

[Example 26]
(Preparation of Colored Composition 26)
After stirring and mixing the mixture of the following composition so as to be uniform, using Eiger Mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) as a media type wet disperser using zirconia beads with a diameter of 0.5 mm After dispersing for 4 hours, the solution was filtered through a filter with a pore size of 5 μm to prepare a colored composition 26.
DIC Corporation C.I. I. Pigment Green 58 (Fastgen Green A 350) 6.0 parts Yellow pigment (PY-1) 9.8 parts Yellow pigment (PY-2) 4.2 parts Acidic dispersant P1 12.5 parts Basic dispersant Q1 10. 0 part Acrylic resin solution 1 21.5 parts Organic solvent (PGMAc) 102.9 parts Photopolymerizable monomer 3.0 parts ("ALONIX M402" manufactured by Toagosei Co., Ltd.)

Comparative Example 1
(Preparation of Colored Composition 27)
After stirring and mixing the mixture of the following composition so as to be uniform, using Eiger Mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) as a media type wet disperser using zirconia beads with a diameter of 0.5 mm It disperse | distributed for 4 hours, and produced coloring composition 27-1.
DIC Corporation C.I. I. Pigment Green 58 (Fast Gen Green A 350) 20.0 parts Acidic dispersant P1 12.5 parts Basic dispersant Q1 10.0 parts Acrylic resin solution 1 21.5 parts Organic solvent (PGMAC) 102.9 parts

Moreover, after stirring and mixing the mixture of the following composition so that it may become uniform, Eiger mill ("Mini model M-250 MKII" by Eiger Japan Co., Ltd.) is manufactured as a media type wet disperser using zirconia beads with a diameter of 0.5 mm. The mixture was dispersed for 4 hours to prepare a coloring composition 27-2.
Yellow pigment (PY-1) 20.0 parts Acidic dispersant P1 12.5 parts Basic dispersant Q1 10.0 parts Acrylic resin solution 1 21.5 parts Organic solvent (PGMAc) 102.9 parts

Moreover, after stirring and mixing the mixture of the following composition so that it may become uniform, Eiger mill ("Mini model M-250 MKII" by Eiger Japan Co., Ltd.) is manufactured as a media type wet disperser using zirconia beads with a diameter of 0.5 mm. The mixture was dispersed for 4 hours to prepare a coloring composition 27-3.
Yellow pigment (PY-2) 20.0 parts Acidic dispersant P1 12.5 parts Basic dispersant Q1 10.0 parts Acrylic resin solution 1 21.5 parts Organic solvent (PGMAC) 102.9 parts

  The obtained coloring composition 27-1 and 27-2 and 27-3 are mixed in a ratio of 6.0: 9.8: 4.2 on a mass basis, filtered through a filter with a pore diameter of 5 μm, and a coloring composition 27 was produced.

Comparative Example 2
(Preparation of Colored Composition 28)
The obtained coloring composition 27-1 and 27-2 and 27-3 are mixed in a ratio of 14.0: 4.2: 1.8 on a mass basis, filtered through a filter with a pore diameter of 5 μm, and a coloring composition 28 was produced.

Comparative Example 3
(Preparation of Colored Composition 29)
After stirring and mixing the mixture of the following composition so as to be uniform, using Eiger Mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) as a media type wet disperser using zirconia beads with a diameter of 0.5 mm It disperse | distributed for 4 hours, and produced coloring composition 29-1.
Green pigment (PG-2) 20.0 parts Acidic dispersant P1 12.5 parts Basic dispersant Q1 10.0 parts Acrylic resin solution 1 21.5 parts Organic solvent (PGMAC) 102.9 parts

  The obtained coloring compositions 27-1 and 29-1 and 27-2 and 27-3 are mixed in a ratio of 4.0: 2.0: 9.8: 4.2 on a mass basis, and the pore size is 5 μm. The mixture was filtered through a filter to make a colored composition 29.

<Evaluation of coloring composition>
Evaluation of the viscosity stability (initial viscosity, viscosity increase rate over time), contrast ratio, and lightness of the obtained coloring composition 1-29 was performed by the following method. The results are shown in Table 2.

(Viscosity stability evaluation)
The viscosity stability of the coloring composition was evaluated by the viscosity increase rate over time.
The initial viscosity of the obtained coloring composition was measured on the day when the coloring composition was prepared, using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.) at a temperature of 25 ° C and a rotation speed of 20 rpm. did.
In addition, the temporal viscosity of the coloring composition is determined by leaving the coloring composition at 40 ° C. for one week, and then using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.), temperature 25 ° C., rotational The viscosity was measured at several 20 rpm. The measured initial viscosity and the temporal viscosity were applied to the following equation to measure the temporal viscosity increase rate.
[Temporal viscosity increase rate] = (temporal viscosity / initial viscosity) × 100 (%)
The evaluation results were judged as follows.
◎: 97.5% or more and less than 102.5% (very good)
○: 95.0% or more and less than 97.5% or 102.5% or more and less than 105.0% (good)
X: less than 95.0% or 105.0% or more (defect)

(Contrast ratio, lightness evaluation)
Coloring compositions 27-1 and 27-2 are added to the obtained coloring compositions 1 to 26 so that the ratio of the green coloring composition to the yellow coloring composition is 7: 3, and the diameter is 0.5 mm. Dispersed and mixed for 10 minutes using beads as a media type wet disperser using an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) to prepare coloring compositions 30 to 55 for evaluation.
Coloring compositions 27-1 and 27-2 are added to the obtained coloring compositions 27 to 29 so that the ratio of the green coloring composition to the yellow coloring composition is 7: 3, and 10 using a disper. The mixture was stirred and mixed for a minute to prepare colored compositions 56 to 58 for evaluation.

<Contrast ratio (CR)>
The resulting coloring composition 30 to 58 is applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 5 minutes, and then heated at 230 ° C. for 20 minutes The coated substrate was produced by leaving it to cool. The contrast ratio and the brightness of the obtained coated substrate were measured. At this time, light emitted from the backlight unit for liquid crystal display passes through the polarizing plate and is polarized, passes through the coating film of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, light passes through the polarizing plate if the polarizing planes of the polarizing plate and the polarizing plate are parallel, but light is blocked by the polarizing plate if the polarization planes are orthogonal to each other. However, when light polarized by the polarizing plate passes through the coating film of the coloring composition, the pigment particles cause scattering or the like, and when a part of the polarization plane is deviated, it transmits when the polarizing plate is parallel. The amount of light decreases, and part of the light is transmitted when the polarizing plates are orthogonal. The transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness when the polarizing plate was parallel to the brightness when orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (brightness in parallel) / (brightness in orthogonal)

Therefore, when scattering is caused by the pigment in the coating, the brightness in parallel decreases and the brightness in orthogonal increases, so the contrast ratio decreases. A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as a luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as a polarizing plate. In the measurement, it measured through the black mask which opened the 1-cm square hole in the measurement part.
After heat treatment at 230 ° C., the coating conditions of the spin coater were adjusted so that the film thickness measured using a surface shape measuring apparatus “Dektak 8 (manufactured by Veeco)” would be 1 μm, and a coating film was formed.
The contrast ratio evaluation results were determined using BLANK 50000 as follows.
: 1: 15,000 or more (very good)
○: 13500 or more and less than 15000 (good)
X: less than 13500 (defective)

<Brightness evaluation>
The lightness Y (C) was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) using the substrate manufactured by the contrast ratio evaluation. The lightness means Y in the Yxy color system. The lightness Y (C) of the coating was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.).
The lightness evaluation results were judged as follows.
:: 77 or more (very good)
○: 70 or more and less than 77 (good)
X: less than 70 (defective)

The evaluation results are shown in Table 2. PG 58 in Table 2 is C.I. I. Pigment green 58 (Fast Gen Green A 350).

  As shown in Table 2, the coloring composition co-dispersed by using three or more kinds of the green pigment and the yellow pigment disperses the green pigment and the yellow pigment separately, and compared with the coloring composition in which the green pigment and the yellow pigment are mixed, CR and lightness It can be seen that a good colored composition can be produced because of the high color stability and the excellent temporal stability.

[Example 27]
(Preparation of Colored Curable Composition 1)
A mixture of the following composition was uniformly stirred and mixed, and then filtered through a filter with a pore size of 1 μm to prepare a colored curable composition 1.
Coloring composition 30 60.0 parts Photopolymerizable monomer 3.0 parts ("Alonics M402" manufactured by Toagosei Co., Ltd.)
Acrylic resin solution 1 14.9 parts Photopolymerization initiator 1.6 parts ("Irgacure 379" manufactured by BASF Japan Ltd.)
Organic solvent 20.4 parts (propylene glycol monomethyl ether acetate)
Antioxidant 0.1 part (pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate])

[Examples 28 to 52 and Comparative Examples 4 to 6]
(Preparation of Colored Curable Composition 2 to 29)
Colored curable compositions 2 to 29 were prepared in the same manner as the colored curable composition 1 except that the colored composition in the method of preparing the colored curable composition 1 was changed as shown in Table 3.

(Coloring evaluation)
The tinting strength was evaluated by the film thickness when the obtained colored curable composition was coated at a specific chromaticity. The colored curable composition 1 to 29 is applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that y = 0.60, and dried at 70 ° C. for 5 minutes, and then The coated substrate was produced by heating at 230 ° C. for 20 minutes and leaving to cool. The obtained coated substrate was measured using a surface shape measuring apparatus "Dektak 8 (manufactured by Veeco)".
The film thickness evaluation results were determined as follows.
◎: less than 1.4 μm (very good)
:: 1.4 μm or more and less than 1.6 μm (good)
X: 1.6 μm or more (defect)

(Evaluation of solvent resistance)
The solvent resistance was evaluated by the film reduction rate.
Each substrate obtained by the above-mentioned evaluation of coloring strength was immersed in a 25 ° C. NMP solution for 10 minutes. Here, "NMP" means N-methyl-2-pyrrolidone. From the film thickness before and after immersion in the NMP solution, measure the same place as the place where the film thickness was measured by the coloring strength evaluation using the surface shape measuring apparatus "Dektak 8 (manufactured by Veeco)". The film reduction rate was calculated by the following equation and compared. Further, each substrate surface was visually observed with a 50 × optical microscope and judged as follows. In addition, a crack means the crack which generate | occur | produced on the coating-film surface.
Film reduction rate = 100 × (film thickness before immersion in NMP solution−film thickness after immersion in NMP solution) / (film thickness before immersion in NMP solution) (%)
◎: no surface crack, less than 10% film reduction (very good)
○: no surface cracks, film reduction rate 10% or more (good)
X: Surface cracked (defective)

(Developability evaluation)
The colored curable composition 1 was coated on the substrate by a spin coater to a film thickness of 1.5 μm to form a colored film. The film was irradiated with ultraviolet light of 300 mJ / cm ² through a photomask using an extra-high pressure mercury lamp. Next, after spray development with an alkaline developer consisting of a 0.2% by mass aqueous solution of potassium hydroxide to remove an unexposed area, the substrate is washed with ion exchanged water and heated at 230 ° C. for 20 minutes to obtain a green filter. A pattern of segments was formed. The colored curable compositions 2 to 29 of the present invention were used to form a green filter segment pattern in the same manner. The film thickness at the same place was measured before and after development, and it was judged as follows from the film thickness difference calculated by the following equation.
Film thickness difference = 100 × (film thickness before development−film thickness after development) / (film thickness before development) (%)
:: Film thickness difference within 20% (very good)
○: film thickness difference greater than 20%, within 40% (good)
X: The film thickness difference is larger than 40%. Or chipping and peeling occur (defect)

  The evaluation results are shown in Table 3.

  As shown in Table 3, a colored curable composition co-dispersed by using three or more types of green pigment and yellow pigment is compared with the colored curable composition in which the green pigment and the yellow pigment are separately dispersed and mixed. Since the film thickness is thin, the solvent resistance is good, and the film thickness difference before and after development is small, it is possible to produce a good colored curable composition. This colored curable composition can be suitably used for a color filter, a solid-state imaging device, and the like.

Claims (3)

  Co-dispersing at least one or more types of green pigment and at least one or more types of yellow pigment such that the total of the types of the green and yellow pigments is 3 or more, and co-dispersing using a dispersing machine The manufacturing method of the coloring composition for color filters which is characterized.   The method for producing a coloring composition for color filter according to claim 1, wherein a basic dispersant, an acidic dispersant and a binder resin are further added and codispersed.   The manufacturing method of the coloring curable composition for color filters which adds a polymerizable monomer further to the coloring composition for color filters manufactured by the manufacturing method of Claim 1 or 2.