JP2019112537A - Coloring agent for color filter, coloring composition and color filter - Google Patents

Abstract

To provide a coloring agent and coloring composition excellent in high brightness, dispersion stability, heat resistance, development property and adhesion, and a color filter having high brightness and high contrast ratio and excellent reliability.SOLUTION: There are provided a coloring agent for color filter contains an isoindoline pigment (A) represented by C. I. PY139 and an isoindoline compound (B) represented by formula, and a coloring composition formed of a binder resin (C) and an organic solvent (D). In formula, R1 and R2 represent H, an alkyl group, an aryl group and a heterocyclic group.SELECTED DRAWING: None

Description

  The present invention relates to a coloring agent for color filters, a coloring composition, and a color composition for use in the manufacture of color filters for use in color liquid crystal display devices, solid-state imaging devices, organic EL display devices, electronic paper and the like. Color filters.

  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 for televisions, personal computer monitors, etc. The demand for high brightness and high color reproducibility is increasing.

  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.

  The quality items required for color filters include contrast ratio and lightness. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state) when light leaks or light must be transmitted (ON) In the state, the transmitted light is attenuated, resulting in a blurred screen. Therefore, in order to realize a high quality liquid crystal display device, it is essential to increase the contrast ratio.

  Furthermore, as described above, color liquid crystal devices are used in televisions, personal computer monitors, etc., and therefore there is an increase in requirements for wide color reproduction area and high reliability as well as high contrast ratio and high brightness for color filters. .

  While demand for high color reproduction is increasing in color filters, there is a problem that when conventional pigments are used, the film thickness of the color filter is increased to improve color reproduction. Therefore, C.I. I. Pigment yellow 139 or C.I. I. Attention is focused on isoindoline pigments represented by C.I.

  Isoindoline pigments are printing inks such as offset ink, gravure ink and inkjet ink, coloring agents such as plastics and paints, image recording materials such as thermal transfer system and electrophotographic system, liquid crystal, plasma, organic electroluminescence (electroluminescence) It is widely used in various applications such as elements, image display devices such as electronic paper, and color filters used for imaging elements such as CCDs.

  Among isoindoline pigments, C.I. I. Pigment Yellow 139 has attracted attention. However, C.I. I. Although pigment yellow 139 exhibits high coloring power, it has a problem that the contrast ratio is low when it is used for a color filter. Therefore, in order to improve the contrast ratio, it is necessary to reduce the primary particle diameter of the pigment as much as possible and reduce the light scattering by the pigment.

  As a method of refining the primary particle diameter of the pigment, a method using fine salt or acrylic resin in the solvent salt milling step, and a method of growing particles after dry pulverization have been proposed (patent documents 1 and 2) , 3). However, C.I. I. Pigment yellow 139 is not sufficiently refined, and C.I. pigment C.I. I. Pigment Yellow 139 was not obtained. Even when this pigment is used in a color filter, the contrast ratio is low and it can not meet the high performance requirements from the market, and further miniaturization is required.

JP 2007-238852 A JP, 2009-256615, A JP 2004-35628 A

  The problem to be solved by the present invention is to solve the low contrast ratio, which is the biggest problem when using isoindoline pigments. Further, the present invention provides a coloring agent and coloring composition containing an isoindoline pigment (especially, CI pigment yellow 139), which enables high lightness, dispersion stability, heat resistance, developability and adhesion. It is an object of the present invention to provide a color filter having a high degree of high contrast ratio and excellent reliability.

  The present inventors have intensively studied to solve the above problems, and as a result, isoindoline pigments (especially C. I.) containing an isoindoline compound (B) having a structure represented by the general formula (1). Pigment yellow 139) is a product of the present invention which has been found to solve the above problems.

（式中、Ｒ₁ および Ｒ₂は水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよい複素環基、置換基を有してもよいシクロアルキル基を表し、Ｒ₁とＲ₂がいずれも水素原子の場合を除く。） That is, an embodiment of the present invention relates to a colorant for a color filter, comprising at least an isoindoline pigment (A) and an isoindoline compound (B) represented by the following general formula (1).

(Wherein, R ₁ and R _{2 each} represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a substituent Represents a cycloalkyl group which may be possessed, except when R ₁ and R ₂ are both hydrogen atoms.

  In addition, the isoindoline pigment (A) is C.I. I. Pigment Yellow 139, and relates to the colorant for color filter described above.

  The present invention also relates to a coloring composition comprising at least a coloring agent, a binder resin (C) and an organic solvent (D), wherein the coloring agent comprises the coloring agent for color filter.

  The present invention also relates to the coloring composition for color filter, which further comprises a photopolymerizable monomer (E) and / or a photopolymerization initiator (F).

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

  The present invention also relates to a liquid crystal display device including the color filter.

  A coloring composition and a coloring composition using the isoindoline compound of the present invention show high contrast ratio, lightness and heat resistance, and a coloring composition excellent in dispersion stability, developability and adhesion of pigment, photosensitive coloring composition I was able to provide something.

Hereinafter, the present invention will be described in detail.
In addition, in this specification, when it describes with "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide", Unless otherwise stated, 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 represents ".
In addition, “CI” listed in the present specification means a color index (CI).

<Colorant>
In the coloring composition for color filters of the present invention, an isoindoline pigment is essential as a coloring agent in order to make high coloring power and high color reproduction compatible.
In addition to the above pigments, the coloring composition for color filters of the present invention may be a red pigment such as a diketopyrrolopyrrole type, anthraquinone type, perylene type, pyranthrone type, or azo type, in order to adjust the chromaticity. Yellow pigments such as quinophthalone and anthraquinone can be incorporated.

<Isoindoline pigment (A)>
As the isoindoline pigment used in the present invention, a generally commercially available isoindoline pigment can be used alone or in combination of two or more kinds, and a dye, a natural pigment and an inorganic pigment can be used in combination. The isoindoline pigment may be refined by salt milling, acid pasting or the like.

  As the isoindoline pigment used in the present invention, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, and C.I. I. Pigment brown 38, C.I. I. Pigment orange 66, C.I. I. Pigment orange 69, C.I. I. Pigment red 260. Among them, C.V. that conforms to the color characteristics of the isoindoline compound (B) described later. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment red 260 is preferable, and C.I. I. Pigment yellow 139 is more preferred

式中、Ｒ₁ および Ｒ₂は水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよい複素環基、置換基を有してもよいシクロアルキル基を表し、Ｒ₁とＲ₂がいずれも水素原子の場合を除く。 <Isoindoline Compound (B)>
The isoindoline compound represented by the following general formula (1) will be described.

In the formula, R ₁ and R _{2 each} have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, and a substituent And R ₁ and R ₂ each independently represent a hydrogen atom.

  As the alkyl group which may have a substituent, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group, Besides linear or branched alkyl groups such as stearyl group and 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2, 2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, diethylaminoethyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, The alkyl group which has substituents, such as 4-methoxy benzyl group, 4-nitro benzyl group, 2,4- dichloro benzyl group, is mentioned.

  Examples of the aryl group which may have a substituent include aryl groups such as phenyl group, naphthyl group and anthranyl group, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group and p-methoxyphenyl group. Group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group And aryl groups having a substituent such as anthraquinonyl group and 2-aminoanthraquinonyl group.

Examples of the heterocyclic group which may have a substituent include pyridyl, pyrazyl, piperidino, pyranyl, morpholino, acridinyl, 3-methylpyridyl, N-methylpiperidyl, N-methylpyrrolyl and the like. It can be mentioned.

  Examples of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2,5-dimethylcyclopentyl group, and a 4-tert-butylcyclohexyl group.

  The above-mentioned substituents greatly affect the strength of the intermolecular hydrogen bond of the isoindoline compound (B), and also affect the heat resistance and color characteristics of the isoindoline compound (B). Therefore, in the viewpoint of heat resistance among the above-mentioned substituents, an alkyl group which may have a substituent is preferable, and a linear alkyl group containing a methyl group and a tert-butyl group is more preferable. From the viewpoint of color characteristics of the isoindoline compound (B), an alkyl group which may have a substituent and a cycloalkyl group which may have a substituent are preferable.

  The isoindoline pigment contained in the coloring composition for color filter of the present invention preferably has an average primary particle diameter in the range of 10 to 50 nm in order to realize high brightness and high contrast ratio of the color filter. . The average primary particle size of the pigment can be measured by transmission electron microscopy. When the average primary particle diameter of the pigment is larger than 50 nm, the lightness and contrast ratio of the color filter become low, and when smaller than 10 nm, the pigment dispersion is very difficult, and the flowability as a coloring composition is secured. Is difficult. As a result, the lightness and contrast ratio of the color filter tend to deteriorate.

(Other pigments)
As a pigment which can be used for the coloring composition of this invention, as a red pigment, C.I. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 81, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 , 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. As an orange pigment which works similarly to a red pigment, for example, C.I. I. Orange pigments such as pigment orange 36, 38, 43, 51, 55, 59, 61 can be used.

  Examples of yellow pigments that can be used in the present invention include C.I. I. Pigments yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 168, 169, 170, 171, 172, 173, 174, 175, 17 , 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or Patent No. 4993026 or the like However, the present invention is not particularly limited thereto. In addition, yellow dyes such as quinoline type, azo type, methine type, coumarin type and isoindoline type can also be used.

  Green pigments that can be used in the present invention are, for example, C.I. I. Pigment Green 7, 10, 36, 37, 58, JP 2008-19383, JP 2007-320986, JP 2004-70342, WO 2015/118720, and the like. Examples thereof include, but are not particularly limited to, pigments, and the like. Further, blue-green dyes such as triarylmethanes, phthalocyanines and squaryliums can also be used.

  Blue pigments that can be used in the present invention are, for example, C.I. I. Pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP-A-2004-333817, Although the aluminum phthalocyanine pigment etc. which are described in the patent 4893859 grade | etc., Are mentioned, it is not limited in particular in these.

  Purple pigments which can be used in the present invention are, for example, C.I. I. Pigment Violet 1 1: 1, 2, 2: 2, 3: 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 25, 29, 31, 32, Examples thereof include 37, 39, 42, 44, 47, 49, 50 and the like, but not limited thereto.

  The content of the pigment used in the red coloring composition of the present invention is preferably 30% by mass or less, more preferably 0.5 to 30% by mass, with respect to the total solid content of the coloring composition.

<Fined pigment>
The coloring composition for color filters of the present invention, when used as a coloring composition, provides fineness of particles by, for example, salt milling treatment as needed to obtain high brightness, contrast ratio and coloring power. It can be suitably used as a filter colorant. The primary particle diameter of the colorant is preferably 10 nm or more in order to enhance the dispersibility in the colorant carrier. Further, in order to obtain a filter segment having high brightness and contrast ratio, the thickness is preferably 50 nm or less.

  As a means to reduce the primary particle diameter of the pigment, a method of mechanically pulverizing the pigment (referred to as grinding method), the one dissolved in a good solvent is added to the poor solvent to precipitate the pigment of the desired primary particle diameter. There are a method (referred to as precipitation method) and a method of producing a pigment having a desired primary particle diameter at the time of synthesis (referred to as synthetic precipitation method). Depending on the synthesis method and the chemical properties of the pigment used, the selection can be carried out by selecting an appropriate method for each pigment. Each method is described below.

In the grinding method, the pigment is mechanically kneaded together with a grinding agent such as water-soluble inorganic salt such as sodium chloride and a water-soluble organic solvent which does not dissolve it (hereinafter, this process is salted using a ball mill, sand mill or kneader) After milling, the inorganic salt and the organic solvent are removed by washing with water and dried to obtain a pigment having a desired specific surface area. However, since crystal growth of the pigment may occur due to the salt milling process, a method of preventing crystal growth is effective by adding a solid resin which is at least partially dissolved in the water-soluble organic solvent at the time of the treatment and a dispersing aid described later. It is.
With regard to the ratio of the pigment to the inorganic salt, when the ratio of the inorganic salt is increased, the refining efficiency of the pigment is improved, but the throughput of the pigment is reduced, so that the productivity is reduced. Generally, 1 to 30 parts by mass, preferably 2 to 20 parts by mass of the inorganic salt is used based on 1 part by mass of the pigment.

In addition, the water-soluble organic solvent is added so that the pigment and the inorganic salt form a uniform mass, and although it depends on the compounding ratio of the pigment and the inorganic salt, usually an amount of 50 to 300% by mass of the pigment is used Be
To explain the grinding method in more detail, a small amount of water-soluble organic solvent is added as a wetting agent to the mixture of pigment and water-soluble inorganic salt, and the mixture is strongly kneaded with a kneader etc. The mixture is stirred with a mixer or the like to form a slurry. Next, the slurry is filtered, washed with water and dried to obtain a pigment having a desired primary particle size.

  The precipitation method is a method in which a pigment is dissolved in an appropriate good solvent and then mixed with a poor solvent to precipitate a pigment having a desired primary particle diameter, and the primary type is determined according to the type and amount of solvent, precipitation temperature, precipitation speed, etc. The size of the particle size can be controlled. Generally, since the pigment is hardly soluble in solvents, usable solvents are limited, for example, strongly acidic solvents such as concentrated sulfuric acid, polyphosphoric acid and chlorosulfonic acid or liquid ammonia, bases such as ammonia solution of sodium methylate, etc. Solvents and the like are known.

  As a typical example of the precipitation method, there is an acid pasting method in which a solution in which a pigment is dissolved in an acidic solvent is poured into another solvent and reprecipitated to obtain fine particles. Industrially, the method of injecting a sulfuric acid solution into water is general from the viewpoint of cost. Although the sulfuric acid concentration is not particularly limited, 95 to 100% by mass is preferable. The amount of sulfuric acid used with respect to the pigment is not particularly limited, but if it is small, the solution viscosity is high and the handling is poor, and if it is too large, the pigment processing efficiency is reduced. It is preferable to use The pigment does not have to be completely dissolved. The temperature at the time of dissolution is preferably 0 to 50 ° C., below which the sulfuric acid may be frozen and the solubility also decreases. If the temperature is too high, side reactions are likely to occur. The temperature of the water to be injected is preferably 1 to 60 ° C. When the injection is started above this temperature, it boils due to the heat of solution of sulfuric acid and the work is dangerous. It freezes at the temperature below this. The time for injection is preferably 0.1 to 30 minutes per part of the pigment.

The control of the primary particle diameter of the pigment can be performed in consideration of the degree of particle size regulation by selecting a method combining precipitation method such as acid pasting method and grinding method such as salt milling method. Is more preferable because the fluidity as a dispersion can be secured at this time.
At the time of salt milling or acid pasting, in order to prevent the aggregation of the pigment accompanied by the control of the primary particle diameter, it is also possible to use a dispersing aid such as a dye derivative, a resin type dispersing agent or a surfactant described later. Further, by performing primary particle diameter control in the form of coexistence of two or more types of pigments, even a pigment which is difficult to disperse alone can be finished as a stable dispersion.

The synthetic precipitation method is a method of synthesizing a pigment and simultaneously precipitating a pigment having a desired primary particle size. However, when the produced finely divided pigment is taken out of the solvent, secondary aggregation usually occurs because filtration, which is a general separation method, becomes difficult unless the pigment particles are aggregated to form large secondary particles. It is applied to pigments such as azo pigments that are synthesized with easy aqueous systems.
Furthermore, as a means to control the primary particle diameter of the pigment, the primary particle diameter of the pigment is reduced and dispersed simultaneously by dispersing the pigment for a long time with a high speed sand mill or the like (so-called dry milling method of pulverizing the pigment). It is also possible.

<Binder resin (C)>
The binder resin used for the coloring composition of the present invention disperses, dyes, or penetrates a coloring agent, and includes thermoplastic resins and the like. In the case of using in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl 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 the 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 As a result, the coloring agent is fixed, the heat resistance is improved, and the color fading (the deterioration of the spectral characteristics) due to the heat of the coloring agent can be suppressed. In addition, it also has the effect of suppressing aggregation and precipitation of the colorant component in the development step.

  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.

The weight average molecular weight (Mw) of the binder resin is preferably in order to disperse the colorant preferably as follows:
The range of 5,000 to 100,000 is preferable, and the range of 7,000 to 80,000 is more preferable. The number average molecular weight (Mn) is preferably in the range of 2,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for color filters, a colorant-adsorbing group, a carboxyl group acting as an alkali-soluble group during development, an aliphatic group acting as an affinity group for a colorant carrier and a solvent, The balance of the aromatic group is important for the dispersibility, permeability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mg KOH / g. If the acid value is less than 20 mg KOH / g, the solubility in a developer may be poor, and it may be difficult to form a fine pattern. If it exceeds 300 mg KOH / g, fine patterns may not be left.

  The binder resin is preferably used in an amount of 20 parts by mass or more based on 100 parts by mass of the total mass of the colorant because the film forming property and the various resistances are good. It is preferable to use in an amount of 100 parts by mass or less because it can be expressed.

  As a thermoplastic resin used for binder resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate And polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resin rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Among them, it is preferable to use an acrylic resin.

As a vinyl type alkali soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer, resin which has acidic groups, such as a carboxyl group and a sulfone group, is mentioned, for example. Specifically as an 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, particularly an acrylic resin having an acidic group, is preferably used because it is high in heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins in which an unsaturated ethylenic double bond is introduced by the method (i) or (ii) shown below.

[Method (i)]
As the method (i), for example, to a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers. And the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is added, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an unsaturated ethylenic double bond and a carboxyl group There is a way to introduce it.

  Examples of unsaturated ethylenic monomers having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate And 3,4-epoxycyclohexyl (meth) acrylates, which may be used alone or in combination of two or more. Glycidyl (meth) acrylate is preferred from the viewpoint of the reactivity with the unsaturated monobasic acid in the next step.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted, etc. Monocarboxylic acids and the like can be mentioned, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, which may be used alone or in combination of two or more. I do not mind. The remaining anhydride is obtained by using tricarboxylic acid anhydride such as trimellitic acid anhydride or using tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride, if necessary, such as increasing the number of carboxyl groups. It is also possible to hydrolyze the group. In addition, when tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as a polybasic acid anhydride, the unsaturated ethylenic double bond can be further increased. As a similar method of the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of the carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]
As method (ii), the unsaturated ethylenic monomer having a hydroxyl group is used, and the monomer of another unsaturated monobasic acid having a carboxyl group or the other monomer is copolymerized. There is a method of reacting the isocyanate group of the unsaturated ethylenic monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  As the unsaturated ethylenic monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol (Meth) acrylates or hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate may be mentioned, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and / or butylene oxide etc. to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylates to which (poly) 12-hydroxystearic acid or the like is added can also be used. From the viewpoint of coating foreign matter suppression, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferred.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethylisocyanate or 1,1-bis [(meth) acryloyloxy] ethylisocyanate, but are not limited thereto. Alternatively, two or more types can be used in combination.

(Thermosetting compound)
In the present invention, a thermosetting compound may be further included in combination with the thermoplastic resin which is a binder resin.

  As a thermosetting compound, for example, an epoxy compound and / or a resin, a benzoguanamine compound and / or a resin, a rosin modified maleic acid compound and / or a resin, a rosin modified fumaric acid compound and / or a resin, a melamine compound and / or a resin Examples include urea compounds and / or resins, phenolic compounds and / or resins, but the present invention is not limited thereto.

<Organic solvent (D)>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and infiltrated into the coloring agent carrier, and the coloring film is coated by applying a dry film thickness of 0.2 to 5 μm on a substrate such as a glass substrate. It is preferred to include an organic solvent to facilitate formation. 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 an organic solvent, for example, ethyl lactate, benzyl alcohol, 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, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, n-propyl acetate, o-xylene, o-diethylbenzene, 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, 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 Chill ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol Monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, Acetic acid Propyl, and dibasic acid esters.
These solvents may be used alone or in combination of two or more at an arbitrary ratio as needed.

  Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl from the viewpoint of good dispersibility of colorant, permeability and coatability of coloring composition. It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent is used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the coloring agent because it can adjust the coloring composition to an appropriate viscosity and form a colored film having an intended uniform film thickness. Is preferred.

<Photopolymerizable monomer (E)>
The coloring composition of the present invention can contain a photopolymerizable monomer (E) and / or a photopolymerization initiator (F), and they are added to the coloring composition of the present invention as a photosensitive coloring composition. The photopolymerizable monomer may be a monomer or an oligomer which is cured by ultraviolet light or heat to generate a transparent resin.

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 photopolymerizable compounds can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The content of the photopolymerizable monomer is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 to 300 parts by mass from the viewpoint of photocurability and developability. .

<Photoinitiator (F)>
The photopolymerization initiator used in the present invention is a compound which generates an active species capable of initiating polymerization of the photopolymerizable monomer upon exposure to radiation such as ultraviolet light, visible light, far ultraviolet light, electron beam, X-ray and the like. is there.

As such a photopolymerization initiator, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -One, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) Acetophenones such as methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Compounds; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin iso Benzoin compounds such as ropyl ether or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, -(P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) -s-triazine, 2,4-bis (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, 2, Triazine compounds such as 4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-ben] Oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6) Phosphine compounds such as -trimethyl benzoyl) 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; imidazole compounds; or titanocene compounds are used.
These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The content of the photopolymerization initiator is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 to 150 parts by mass from the viewpoint of photocurability and developability.

(Sensitizer)
Furthermore, the coloring composition for color filters 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 for color filter, and is 5 to 5 from the viewpoint of photocurability and developability. More preferably, it is 50 parts by mass.

(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. Further, the antioxidant used in the present invention is preferably one containing no halogen atom.

  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-piperidyl 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 And poly Mar-type compounds 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- Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like can be mentioned. 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.

  Moreover, content of antioxidant is more preferable in the case of 0.5-5.0 mass% on the basis of solid content mass of a coloring composition, since a spectral characteristic and a sensitivity are favorable.

(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 coloring composition for color filters of the present invention in order to improve the leveling property 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 BYK Chemie, and the like. As a specific example of dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by BYK-Chemie company, BYK-370, etc. are mentioned. 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. Generally, it is preferable to use 0.003 to 0.5% by mass of the leveling agent content in 100% by mass of the total mass of the coloring composition.

  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 polyethylene glycol monolaurate; alkyl betaines such as alkyl dimethylamino acetic acid betaine; amphoteric surfactants such as alkyl imidazolines; 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.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivatives 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-ethyl-4-methylimidazole, etc., phosphorus compounds (eg tri Phenyl phosphine Guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino) Using -S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct, etc. Can. 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.

(Storage stabilizer)
Examples of the storage stabilizer include organic acids such as lactic acid and oxalic acid and methyl ethers thereof, organic phosphines such as t-butyl pyrocatechol, tetraethyl phosphine and tetraphenyl phosphine, and phosphites. 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 colorant.

(Adhesion improver)
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 colorant in the coloring composition.

(Multifunctional thiol)
The coloring composition of the present invention may contain a compound having two or more thiol (SH) groups as a multifunctional thiol.
By using a multifunctional thiol together with a photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates a thiyl radical which is less susceptible to inhibition of polymerization by oxygen, so the resulting colored composition has high sensitivity. It becomes. In particular, polyfunctional aliphatic thiols in which an SH group is bonded to an aliphatic group such as a methylene or ethylene group are preferable. As polyfunctional thiols, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bis thiopropio , Trimethylolpropane tristhioglycollate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethyl mercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dib Arylamino) -4,6-dimercapto--s- triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tris thiopropionate, pentaerythritol tetrakis thiopropionate.

These polyfunctional thiols can be used alone or in combination of two or more.
The content of the multifunctional thiol is preferably 0.05 to 100 parts by mass, and more preferably 1.0 to 50.0 parts by mass with respect to 100 parts by mass of the colorant. If the content of the multifunctional thiol is less than 0.05 parts by mass, the effect of the chain transfer agent is small, and if it is more than 100 parts by mass, the polymerization initiation function is not improved and the developability, adhesion, etc. become insufficient. .

<Coloring composition>
The coloring composition for color filters of the present invention is a method of dispersing an organic pigment in a pigment carrier solution, or a method of dispersing an organic pigment in water or an organic solvent to prepare a pigment dispersion and then mixing it with the pigment carrier solution Manufactured by The method of dispersing the pigment is not particularly limited, but it is possible to use a media type dispersing machine such as a three-roll mill, a two-roll mill, a kneader, a horizontal type of cylindrical dispersing machine, vertical type, or annular type (annular type). The method is preferred.

  Examples of the media-type disperser include various dispersers using media such as a ball mill, a sand mill, an attritor, a vibration mill, and an Eiger mill.

  The rotating shaft of the media type dispersing machine is provided with stirring blades having various shapes, and a disk type, a pin type, etc. are known. Among them, the one having a rotor pin is more effective than the present invention. It is preferable to make it more remarkable.

  Further, as the media separation mechanism, there are a centrifugal separation method, a slit method (gap separator method), a screen method and the like, but a centrifugal separation method is preferable. The production of slits or screens capable of separating fine media having a particle size of 0.3 mm or less is very difficult due to machining accuracy, and the possibility of clogging when supplying a mill base pigment dispersion (kneaded product) There is

  Examples of wet dispersers provided with a rotor pin and a media separation mechanism by centrifugal separation include Super Apex Mill (manufactured by Kotobuki Industry Co., Ltd.), Ultra Apex Mill (manufactured by Kotobuki Industry Co., Ltd.), Dual Apex Mill (manufactured by Kotobuki Industry Co., Ltd.), DCP type There are pearl mill (manufactured by Eirich Co., Ltd.), picoglen mill (manufactured by Asada Iron Works Co., Ltd.), Eco Mill (manufactured by Asada Iron Works Co., Ltd.), and the like.

  In addition, the media filling rate in the dispersing machine with high dispersion efficiency is preferably 50 to 100% by mass, and more preferably 60 to 80% by mass.

The material of the media is not particularly limited, and commonly used glass, steel, stainless steel, ceramic, zircon, zirconia and the like can be mentioned.
<Dispersion aid>
When the colorant is dispersed in the colorant carrier, dispersion aids such as dye derivatives, resin type dispersants, surfactants and the like can be suitably contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the coloring composition formed by dispersing the colorant in the colorant carrier using the dispersion aid has brightness, contrast and storage stability. Sex is good.

  The coloring composition for color filters of the present invention preferably contains a dye derivative. By including the dye derivative, effects such as improvement of the viscosity characteristics of the coloring composition and the physical properties of the coating film are exhibited.

[Dye derivative]
As dye derivatives used in the present invention, known dye derivatives having an acidic group, a basic group, a neutral group and the like in the organic dye residue can be used. For example, a compound having an acidic functional group such as sulfo group, carboxy group or phosphoric acid group, an amine salt thereof, a compound having a basic functional group such as a sulfonamide group or a tertiary amino group at the terminal, a phenyl group or phthalimide The compound which has neutral functional groups, such as an alkyl group, is mentioned. 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 2003-128669, JP 2004-091497, JP 2007-156395, JP 2008-094873, JP 2008-094986, JP 2008-095007, JP 2008 JP-195916-A, Patent No. 4585781-A, JP-2006-291194-A, JP-A-2007-226161, JP-A-2007-314681, JP-A-2007-314785, JP-A-2012-226110 JP-A-2017-165820 and JP-A-2005- 81383 JP, include known dye derivative according to such. In these documents, a dye derivative may be described as a derivative, a pigment derivative, a pigment dispersant or simply a compound, etc. However, the organic dye residue described above may be an acidic group, a basic group, a neutral group, etc. The compound which has a functional group of is synonymous with a pigment derivative. Moreover, these can be used individually or in mixture of 2 or more types. Among these, from the viewpoint of the spectral stability and viscosity stability, the coloring composition of the present invention is preferably a dye derivative in which the matrix skeleton is an organic pigment residue or a triazine residue, and among them, quinophthalone pigments and azo Organic pigment residues or triazine residues which are based pigments or anthraquinone pigments are preferred.
More preferably, they are azo dye derivatives or anthraquinone dye derivatives. By including an azo dye derivative or an anthraquinone dye derivative, the compatibility with the pigment and the resin type dispersant is improved, and the effect of preventing reaggregation of the isoindoline pigment after dispersion is improved. Further, the improvement of the compatibility improves the effect of suppressing the dry aggregation at the time of coating film preparation when the colored composition or the colored curable composition is applied to glass. Therefore, the physical properties of the coating film are improved.

  The content of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more, with respect to 100 parts by mass of the colorant, from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less.

  The pigment derivative is adsorbed on the pigment surface by adding the pigment derivative to the pigment and performing dispersion processing such as wet dispersion using two rolls, three rolls, and beads, and the pigment surface has polarity and adsorption of the resin type dispersant Is promoted, and compatibility with pigments, pigment derivatives, resin type dispersants, solvents, and other additives is improved, and dispersion stability and viscosity stability over time when formed into a colored composition or a colored curable composition are improved. Do. In addition, since the compatibility is improved, the coating film is excellent in the temporal stability of the coating when the colored curable composition is applied to glass, and the waiting time from the application of the colored curable composition to the exposure (PCD: Post Coating Delay) And the stability / characteristic dependency of the pattern shape and the like with respect to the waiting time (PED: Post Exposure Delay) from exposure to heat treatment, and line width sensitivity stability. Furthermore, development time variations and development residues are also suppressed.

[Resin type dispersant]
The coloring composition of the present invention may contain a conventionally known resin-type dispersant.
The resin type dispersant has a colorant affinity site having a property of adsorbing to the additive colorant, and a site compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed in the colorant carrier Work to stabilize the 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 , Polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) with polyester having free carboxyl group, 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 poly Acrylate-based, ethylene oxide / propylene oxide adduct, used phosphoric acid ester and the like, they may be used alone or in combination, is not necessarily limited thereto.

(Basic resin type dispersant)
The dispersant used in the present invention is preferably a basic resin type dispersant having a basic functional group, and a nitrogen atom-containing graft copolymer, a tertiary amino group in the 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 resin-type dispersant is preferably used at about 5 to 200% by mass with respect to the total amount of the colorant, and more preferably about 10 to 100% by mass from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by BIC Chem. Japan. 167, 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, 1300, manufactured by Nippon Lebrizole. , 13240, 13650, 13940, 16000, 17000, 18000, 20000, 20000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32500, 32500, 34750, 35100, 36600, 38500, 41000, 41090, 53095 , 55000, 56000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 453, 454, 4540, 4550, 4560, 4800, 010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of Ajisupa -PA111, PB711, PB821, PB822, PB824, and the like are preferable.

(Acid resin type dispersant)
Moreover, as a resin type dispersing agent used by this invention, an acidic resin type dispersing agent can also be used suitably. As a resin type dispersing agent used by this invention, it is also preferable to contain following (S1) or (S2) as a resin type dispersing agent which has a carboxyl group.
(S1) A resin type 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 Resin type dispersant which is united.

«Resin type dispersant (S1)»
The resin type 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

«Resin type dispersant (S2)»
The resin type dispersant (S2) can be produced by a known method such as JP2009-155406A, JP2010-185934A, JP2011-157416A, etc. For example, a compound having a hydroxyl group By polymerizing the ethylenically unsaturated monomer (r) in the presence of the reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride can get. 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.

[Surfactant]
As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl dimethylamino There may be mentioned amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines, which may be used alone or in combination of two or more, but it is not necessarily limited thereto.

  When a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. When the content of the surfactant is less than 0.1 parts by mass, the added effect is difficult to be obtained, and when the content is more than 55 parts by mass, the dispersing agent may affect the dispersion due to an excess of the dispersing agent. .

<Color filter>
The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. In addition, the color filter may further include a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment.

  Examples of base materials such as transparent substrates constituting color filters include glass plates such as soda lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate. Used. In addition, on the surface of a glass plate or a resin plate, a transparent electrode made of indium oxide, tin oxide or the like may be formed for driving liquid crystal after panelization.

<Method of manufacturing color filter>
The color filter of the present invention can be produced by a printing method or a photolithography method using the above-mentioned coloring composition. 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 low-cost as a manufacturing method of a color filter, and excellent in mass productivity. There is. Furthermore, with the development of printing technology, printing of fine patterns having 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, control of the flowability of the ink on the printing press is also important, and the preparation of the ink viscosity can also be performed by the dispersant and the 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, it is immersed in a solvent or an alkaline developer, or the developer is sprayed by a spray or the like to remove the uncured portion to form a desired pattern. A color filter can be manufactured by repeating the same operation as this for other colors. 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 material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can be performed.

  The color filter of 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 coloring 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 transparent substrate or the 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 which is a liquid crystal display device is manufactured.

  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.

(Polymerization average molecular weight (Mw) of resin)
The polymerization average molecular weight (Mw) of the resin was measured using a TSK gel column (manufactured by Tosoh Corporation) and a GPC equipped with a RI detector (HLC-8120GPC manufactured by Tosoh Corporation), using polystyrene as the developing solvent and polystyrene conversion It is a weight average molecular weight (Mw).

(Preparation of acrylic resin solution)
800 parts of cyclohexanone is put in a reaction vessel, and heated to 100 ° C. while injecting nitrogen gas into the vessel, and 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate, 65.0 parts of butyl methacrylate from the dropping tube at the same temperature. A mixture of 60.0 parts of 2-hydroxyethyl methacrylate and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After dropping, the mixture is further reacted at 80 ° C. for 3 hours, then, a solution of 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone is added, and the reaction is further continued at 80 ° C. for 1 hour to obtain weight average molecular weight A solution of about 40,000 acrylic resins was obtained.
After cooling to room temperature, approximately 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and cyclohexanone is added to the previously synthesized resin solution so that the non-volatile content is 20%. An acrylic resin solution was prepared.

<Method of producing isoindoline pigment (A)>
The preparation method of the isoindoline pigment (A) used for this invention is demonstrated.

(Preparation of Isoindoline Pigment A-1)
C. I. Pigment Yellow 139 ("PARIOTOL ERO D 1819" manufactured by BASF Corp.): 140 parts, sodium chloride: 1400 parts, and diethylene glycol: 260 parts are charged in a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) and mixed at 60 ° C for 8 hours did. Next, the kneaded product is poured into 5 liters of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and drying overnight at 80 ° C. To obtain 135 parts of isoindoline pigment (A-1).

<Method for producing isoindoline compound (B)>
The identification method of the isoindoline compound (B) used for this invention is demonstrated.

(Method for identifying isoindoline compound (B))
Identification of the isoindoline compound (B) of the present invention was obtained from Waters ACQUITY UPLS H-Class (column used: ACQUITY UPLC BEH C18 Column 130 Å, 1.7 μm, 2.1 mm × 50 mm) / Ms TAP XEVO TQD Identification of the obtained compound was performed with agreement between the molecular ion peak of mass spectrum and the mass number obtained by calculation.

Production Example 1 (Production of Isoindoline Compound (B-1))
To 270 parts of water was added 30 parts of glacial acetic acid, to which 11.3 parts of 1,3-dimethylbarbituric acid was added, and the mixture was stirred at 50 ° C. for 1 hour. Subsequently, 5.0 parts of 1,3-diiminoisoindoline was added, and the mixture was stirred at 80 ° C. until the raw material 1,3-diiminoisoindoline disappeared. Disappearance of the raw material was confirmed by UPLC. After cooling to room temperature, 28% aqueous ammonia is added so that the pH is 7.0 to 8.0, the solid content is separated by filtration, washed with 2000 parts of water, and dried at 80 ° C., isoindoline 10.9 parts (yield 75%) of compounds (B-1) were obtained.

Production Example 2
(Production of Isoindoline Compounds (B-2) to (B-5))
A reaction operation is carried out in the same manner as the isoindoline compound (B-1) except that 11.3 parts of 1,3-dimethyl barbituric acid in Production Example 1 is changed to the raw materials shown in Table 1, to obtain an isoindoline compound (B-). 2) to (B-5) were obtained in the yields described in Table 1.

<Preparation of a yellow coloring composition>
Example 1
(Preparation of yellow coloring composition 1 (YP-1))
A mixture consisting of the following components is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads of 0.5 mm in diameter, The mixture was filtered through a filter with a pore size of 5 μm to prepare a yellow coloring composition 1 (YP-1).

Isoindoline pigment (A-1) 9.5 parts Isoindoline compound (B-1) 0.5 part Resin type dispersant ("PB 821" manufactured by Ajinomoto Fine Techno Co., Ltd.) 1.0 part Acrylic resin solution 45.0 parts Propylene 44.0 parts of glycol monomethyl ether acetate

[Examples 2 to 5, Comparative Example 1]
(Preparation of Yellow Colored Composition (YP-2) to (YP-6))
Yellow coloring composition (YP-2 to YP-6) in the same manner as the yellow coloring composition (YP-1) except that the isoindoline compound (B-1) is changed to the isoindoline compound described in Table 2. Was produced.

<Evaluation of yellow coloring composition>
The evaluation of the yellow coloring composition was performed by producing a coating film using the yellow coloring composition, and measuring the brightness, the contrast ratio, and the heat resistance. The evaluation method is shown below, and the evaluation results are shown in Table 3.

(Brightness evaluation)
The yellow coloring composition was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and a coating film was obtained by heating at 230 ° C. for 20 minutes. At this time, after the heat treatment at 230 ° C., the film thickness of the coating film was coated by appropriately changing the coating conditions (the number of rotations of the spin coater, time) so that x = 0.440 in the C light source. The lightness (Y) of the resulting coated film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), and judged according to the following criteria.

○: 89.0 or more (good)
:: 87.5 or more and less than 89.0 (practical level)
X: less than 87.5 (not available level)

(Contrast ratio evaluation)
The light emitted from the liquid crystal display backlight unit is polarized through the polarizing plate, passes through the coating 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 colorant particles cause scattering or the like, and when a part of the polarization plane is deviated, transmission occurs when the polarizing plates are parallel. The amount of light to be reduced decreases, and when the polarizing plates are orthogonal, some light is transmitted. 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 occurs due to the coloring agent in the coating film, 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. It judged according to the following standard using the same coating film as what carried out lightness evaluation.

○: 3000 or more (good)
:: 2000 or more and less than 3000 (practical level)
X: less than 2000 (not available level)

(Evaluation of heat resistance)
The prepared color filter is forcibly heat treated in an oven at 250 ° C. for 1 hour, and the contrast ratio retention ratio before and after the treatment (= contrast ratio after heat treatment / contrast ratio before heat treatment × 100 (%) Was evaluated and judged according to the following criteria.

○: 95% or more (good)
:: 85% or more and less than 95% (practical level)
X: less than 85% (not available level)

  From Table 3, it became clear that the coloring composition of Examples 1-5 using the isoindoline compound represented by General formula (1) is excellent in a lightness, contrast ratio, and all viewpoints of heat resistance. . On the other hand, it became clear that the coloring composition of the comparative example 1 which does not contain the iso indoline compound represented by General formula (1) is inferior in a brightness, contrast ratio, and heat resistance to an Example.

<Preparation of green, red and blue coloring compositions>
Production of micronized green pigment (G-1) Phthalocyanine-based green pigment C.I. I. Pigment Green 58 ("FASTOGEN GREEN A110" manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried overnight at 85 ° C. to obtain a finely divided green pigment (G-1).

(Preparation of green coloring composition (GP-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads of 0.5 mm in diameter. Thereafter, the obtained mixture was filtered with a filter having a pore diameter of 5.0 μm to prepare a colored composition (GP-1) having a nonvolatile component of 20% by mass.

Fine green pigment (G-1) 10.0 parts Resin type dispersant ("EFKA 4300" manufactured by BASF Japan Ltd.) 1.0 part Acrylic resin solution 45.0 parts Propylene glycol monomethyl ether acetate 44.0 parts

(Production of micronized yellow pigment (Y-2))
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 ("Paliotol Yellow L 0962 HD" manufactured by BASF Corporation), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. And finely divided yellow pigment (Y-2) were obtained.

(Preparation of yellow coloring composition (YP-7))
A mixture consisting of the following components is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads of 0.5 mm in diameter, The mixture was filtered through a filter with a pore size of 5 μm to prepare a yellow coloring composition 1 (YP-7).

Refined yellow pigment (Y-2) 10.0 parts Resin type dispersant ("PB 821" manufactured by Ajinomoto Fine Techno Co., Ltd.) 1.0 part Acrylic resin solution 45.0 parts Propylene glycol monomethyl ether acetate 44.0 parts

Production of micronized blue pigment (B-1) Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 ("LIONOL BLUE ES" manufactured by Toyo Color Co., Ltd., specific surface area 60 m ² / g) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts in a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) And kneading at 80 ° C. for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, water washing was repeated to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. to obtain a finely divided blue pigment (B-1).

Preparation of micronized purple pigment (V-1) Dioxazine purple pigment C.I. I. Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Color Corp.), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried overnight at 85 ° C. to obtain finely divided purple pigment 1 (V-1).

Preparation of coloring composition (BP-1)
The mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads of 0.5 mm in diameter. Thereafter, the obtained mixture was filtered with a filter having a pore diameter of 5.0 μm to prepare a colored composition (BP-1) having a non-volatile component of 20% by mass.

Refined blue pigment (B-1) 7.2 parts Refined purple colorant (V-1) 4.8 parts Resin type dispersant ("EFKA 4300" manufactured by BASF Japan Ltd.) 1.0 part acrylic resin solution 35.0 50.0 parts of propylene glycol monomethyl ether acetate

(Production of finely divided red pigment R-1)
Anthraquinone red pigment C.I. I. Pigment Red 177 ("Chromophthal Red A2B" manufactured by BASF Corporation), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , Anthraquinone-based finely divided red pigment (R-1) was obtained.

(Production of Red Colored Composition (RP-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads of 0.5 mm in diameter. Thereafter, the obtained mixture was filtered with a filter having a pore diameter of 5.0 μm to prepare a colored composition (RP-1) having a nonvolatile component of 20% by mass.

Refined red pigment (R-1) 10.0 parts Resin type dispersant ("EFKA 4300" manufactured by BASF Japan Ltd.) 1.0 part Acrylic resin solution 45.0 parts Propylene glycol monomethyl ether acetate 44.0 parts

[Example 6]
(Red photosensitive coloring composition (RR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore size of 1 μm to prepare a red photosensitive coloring composition (RR-1).

Red coloring composition (RP-1) 33.6 parts Yellow coloring composition (YP-1) 8.4 parts acrylic resin solution 1 13.2 parts photopolymerizable monomer ("Alonix M400" manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator ("IRGACURE 907" manufactured by BASF Japan Ltd.) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 parts ethylene glycol monomethyl ether acetate 39. 6 copies

[Examples 7 to 10, Comparative Example 2]
Photosensitive coloring compositions (RR-2) were prepared in the same manner as in Example 6, except that the yellow coloring composition (YP-1) in Example 6 was changed to the yellow coloring composition shown in Table 4 by mass. ) To (RR-6).

<Evaluation of red photosensitive coloring composition>
The developability, dispersion stability, and adhesion of the obtained red photosensitive coloring composition were evaluated by the following methods. The results are shown in Table 5.

(Evaluation of developability)
Using the red photosensitive coloring composition obtained, a spin coater was used to apply a film thickness of 2.0 μm on a 100 mm × 100 mm, 1.1 mm thick glass substrate, and the film thickness was 20 μm at 70 ° C. It dried for a minute and produced the coating film board | substrate. The substrate was spray-developed with a 0.2% by mass aqueous solution of sodium carbonate at 23 ° C., and the time (development time) in which development was performed until the coating film was completely eliminated was calculated, and the developability was evaluated. The judgment criteria are shown below.

:: less than 20 seconds: good ○: more than 20 seconds and less than 30 seconds: practicable ×: 30 seconds or more: unusable level

(Viscosity characteristics (dispersion stability))
The viscosity of the red photosensitive coloring composition was measured with an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and an initial viscosity at 50 rpm. Separately, 25 g of the red photosensitive coloring composition was allowed to stand at 40 ° C. for 24 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as above to obtain the temporal viscosity.
Dispersion stability was evaluated on the basis of the following by viscosity change rate = (initial viscosity-viscosity over time) / initial viscosity x 100 (%). ◎ is a practically good level, レ ベ ル is a practicable level, and x is a level not suitable for practical use.

◎: When the viscosity change rate was within ± 10% and no sediment was generated.
○: When the viscosity change rate exceeds ± 10% and is within 20%, no sediment is generated.
X: When the rate of viscosity change exceeds ± 20%, or when the rate of change in viscosity is within ± 20%, precipitation occurs.

(Evaluation of adhesion)
The substrate coated with a red photosensitive coloring composition on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater at a rotational speed of 2 μm after drying is dried at 70 ° C. for 20 minutes After that, 150 mJ / cm ² of ultraviolet light was irradiated using a super high pressure mercury lamp through a photomask having 100 openings of 10 μm × 10 μm. Subsequently, after spray development was carried out with an alkaline developing solution consisting of a 0.2% by mass aqueous solution of sodium carbonate to remove an unexposed part, the resultant was washed with ion exchanged water. At this time, the adhesion was evaluated based on how many 10 μm × 10 μm patterns remain. Further, the evaluation of developability was judged according to the following criteria.

:: 90 or more patterns left (good)
○: 70 to 89 patterns remain (practical level)
×: 0 to 69 patterns remaining (unavailable level)

  From Table 5, the red photosensitive coloring compositions of Examples 6 to 10 using the isoindoline compound represented by the general formula (1) have excellent developability and dispersion stability, and high adhesion on the substrate. It became clear. On the other hand, the colored composition of Comparative Example 2 not using the isoindoline compound represented by the general formula (1) was found to be inferior in developability and dispersion stability, and also in low adhesion on the substrate.

<Preparation of color filter>
The red photosensitive coloring composition of the present invention was used to prepare a color filter. The green photosensitive coloring composition and the blue photosensitive coloring composition were prepared as follows.

(Preparation of green photosensitive coloring composition 1 (GR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore size of 1 μm to prepare a green photosensitive coloring composition (GR-1).

Green coloring composition (GP-1): 24.8 parts Yellow coloring composition (YP-7): 25.2 parts Acrylic resin solution: 7.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "ALONIX M" -402 "): 2.0 parts Photopolymerization initiator (" IRGACURE 907 "manufactured by BASF Corporation): 1.2 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Industry Co., Ltd.): 0.3 parts cyclohexanone : 39.0 parts

(Preparation of Blue-Photosensitive Colored Composition 1 (BR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore diameter of 1 μm to prepare a blue photosensitive colored composition 1 (BR-1).

Blue colored composition 1 (BP-1) 34.0 parts Acrylic resin solution 15.2 parts Photopolymerizable monomer ("Alonix M400" manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (manufactured by BASF Japan Ltd.) "IRGACURE 907" 2.0 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 parts ethylene glycol monomethyl ether acetate 45.1 parts

Example 11 Color Filter (CF-1)
The red photosensitive coloring composition (RR-1) of the present invention was applied to a glass substrate on which a black matrix is formed in advance by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. The substrate was then cooled to room temperature, and then exposed to ultraviolet light through a photomask using an extra-high pressure mercury lamp.
Thereafter, the substrate was spray developed for 30 seconds in a 0.2% by mass aqueous solution of sodium carbonate at 23 ° C., washed with ion exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a stripe-shaped red colored pixel layer on the substrate.
Next, using a green photosensitive coloring composition (GR-1), a green colored pixel layer was formed in the same manner as the red colored pixel layer. Furthermore, the blue photosensitive pixel composition was similarly formed using blue photosensitive coloring composition (BR-1), and the color filter (CF-1) was obtained. The formed film thickness of each colored pixel layer was 2.0 μm.

Comparative Example 3 Color Filter (CF-2)
In the preparation of the color filter (CF-1), the same method as (CF-1) is used except that the photosensitive coloring composition used is changed to (RR-6) for the red photosensitive coloring composition. A color filter (CF-2) was produced. The formed film thickness of each colored pixel layer was 2.0 μm.

  When the contrast ratio of (CF-1) and (CF-2) was measured, (CF-1) was an excellent result, and the effect of the present invention was proved.

Claims (6)

A coloring agent for color filter, comprising at least an isoindoline pigment (A) and an isoindoline compound (B) represented by the following general formula (1).
General formula (1)

(Wherein, R ₁ and R _{2 each} represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a substituent Represents a cycloalkyl group which may be possessed, except when R ₁ and R ₂ are both hydrogen atoms. The isoindoline pigment (A) is preferably C.I. I. Pigment yellow 139, and the coloring agent for color filters of Claim 1 characterized by the above-mentioned. A coloring composition comprising at least a coloring agent, a binder resin (C), and an organic solvent (D), wherein the coloring agent comprises the coloring agent for color filters according to claim 1 or 2. Composition. The coloring composition for color filters according to claim 3, further comprising a photopolymerizable monomer (E) and / or a photopolymerization initiator (F). A color filter comprising a filter segment formed from the coloring composition for a color filter according to claim 3 or 4 on a substrate. A liquid crystal display device comprising the color filter according to claim 5.