JP2017068159A - Coloring composition for color filter, color filter, and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring resin composition for a color filter that can achieve red target chromaticity with high color density without an increase in thickness and form red pixels with high luminance, a color filter that includes a red filter segment with high lightness and contrast, and a liquid crystal display including the same.SOLUTION: There is provided a red coloring composition for a color filter that contains a pigment (A), a pigment dispersant (B), and a binder resin (C), where the pigment contains at least three types of pigments: a diketopyrrolopyrrole red pigment, an anthraquinone red pigment, and a benzimidazolone orange pigment.SELECTED DRAWING: Figure 1

Description

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

  In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal display devices has increased. Recently, the penetration rate of home-use liquid crystal televisions is also increasing, and the market for liquid crystal display devices is expanding. Furthermore, liquid crystal display devices that have become widespread in recent years tend to have larger screens, and the tendency is particularly strong for home-use liquid crystal televisions. In such a situation, there is an increasing demand for liquid crystal display devices to further increase brightness and improve color reproducibility.

Many conventional display devices comply with sRGB (IEC 61966-2-1), which is an international standard for color space. However, due to the demand for further improvement in color reproducibility, there is an increasing demand for display devices that support Adobe RGB having a wider color reproduction range than sRGB. The AdobeRGB standard is a color space definition proposed by Adobe Systems. In AdobeRGB, the three primary colors are defined as follows for the chromaticity coordinates x and y in the XYZ color system.
Red: x = 0.64; y = 0.34
Green: x = 0.21; y = 0.71
Blue: x = 0.15; y = 0.06

There is also a DCI (Digital Cinema Initiates) standard having a wider color gamut in the red and green directions than sRGB. The DCI standard is a digital cinema standard of an organization (Digital Cinema Initiative, LCC) created by seven movie studios including Disney, Fox, Metro-Goldwyn-Mayer, Paramount Pictures, Sony Pictures Entertainment, Universal Studios, and Warner Bros. Studios. It is.
The color gamut of the DCI standard includes blue coordinates (x, y) = (0.150, 0.060) and green coordinates (x, y) = (0) in the xy chromaticity diagram of the CIE1931-XYZ color system. .265, 0.690) and a region represented by a triangle connecting three points of red coordinates (x, y) = (0.680, 0.320).

Patent Document 1 discloses a colored resin composition for a color filter that can achieve a green target chromaticity with a high color density and can form a high-luminance green pixel without increasing the thickness.
Patent Document 2 discloses a high color gamut liquid crystal display device that exhibits a good color reproduction range with respect to the color gamut of the DCI standard.
However, for red, no means other than thickening has been obtained when achieving the target chromaticity with a high color density. In other words, the use of a diketopyrrolopyrrole red pigment, which is advantageous for improving brightness, does not provide sufficient contrast, and the film thickness increases, so anthraquinone, which is advantageous for high contrast and thin film formation. A red pigment is used in combination. However, when an anthraquinone red pigment is blended in order to obtain sufficient contrast, sufficient brightness cannot be obtained. In addition, when an anthraquinone red pigment is used in combination for the purpose of thinning the film, the target color is not obtained. Therefore, it is necessary to adjust the chromaticity with a pigment that is yellower than the diketopyrrolopyrrole red pigment. So far, metal complex yellow pigments and quinophthalone yellow pigments have been used as yellow pigments than diketopyrrolopyrrole red pigments. However, a sufficient effect is not obtained for the recent thinning.

JP2013-205581A Japanese Patent Laying-Open No. 2015-087527

The present invention provides a colored resin composition for a color filter that achieves a target chromaticity of red with a high color density without forming a thick film and can form a high-luminance red pixel, and a red filter segment with high brightness and contrast. An object of the present invention is to provide a color filter and a liquid crystal display device including the color filter.

As a result of intensive studies to solve the above problems in consideration of the above problems, the present inventor has developed a red color filter containing a pigment (A), a pigment dispersant (B), and a binder resin (C). In the coloring composition, the above problem is solved by the red coloring composition for a color filter, wherein the pigment (A) contains a diketopyrrolopyrrole red pigment, an anthraquinone red pigment, and a benzimidazolone orange pigment. It has been found that.

  That is, the present invention provides a red coloring composition for a color filter containing a pigment (A), a pigment dispersant (B), and a binder resin (C), wherein the pigment (A) is a diketopyrrolopyrrole-based composition. The present invention relates to a red coloring composition for a color filter, comprising a red pigment, an anthraquinone red pigment, and a benzimidazolone orange pigment.

The content of the three pigments is 30 to 85% by weight of a diketopyrrolopyrrole red pigment, 10 to 60% by weight of an anthraquinone red pigment, and a benzimidazolone orange pigment 5 based on the total weight of the pigment. It is related with the red coloring composition for color filters characterized by being-30weight%.

In the present invention, the content of the three pigments is 30 to 85% by weight of a diketopyrrolopyrrole red pigment, 10 to 60% by weight of an anthraquinone red pigment, benzimidazolone based on the total weight of the pigment. It is related with the red coloring composition for color filters characterized by being 5-30 weight% of a system orange pigment.

Moreover, this invention relates to the color filter characterized by including the red filter segment formed using the red coloring composition for color filters in any one of Claims 1-5.

Moreover, this invention relates to the red coloring composition for color filters in any one of Claims 1-4 characterized by including a photopolymerizable monomer (D) and a photoinitiator (E) further. .

The present invention also relates to a color filter comprising a red filter segment formed using the red coloring composition for a color filter described above.

In the present invention, the liquid crystal display device has a backlight,
The backlight has a wavelength (λ1) at which the emission intensity is maximum within a range of 430 nm to 485 nm, a peak wavelength (λ2) of a second emission intensity within a range of 530 nm to 580 nm, and a wavelength at λ1 The liquid crystal display device according to the above, which is a white LED light source having spectral characteristics in which a ratio (I2 / I1) of the emission intensity I1 to the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less.

Further, according to the present invention, the liquid crystal display device described above has a backlight,
The backlight has a wavelength (λ3) where the emission intensity becomes maximum within a range of 430 nm to 485 nm, has a wavelength (λ4) where the emission intensity becomes maximum within a range of 530 nm to 580 nm, and has a wavelength of 600 nm to 650 nm. A wavelength (λ5) at which the emission intensity becomes maximum within the range, and the ratio (I4 / I3) of the emission intensity I3 at the wavelength λ3 and the emission intensity I4 at the wavelength λ4 is 0.2 or more and 0.4 or less, The present invention relates to a liquid crystal display device which is a white LED light source having spectral characteristics in which a ratio (I5 / I3) of emission intensity I3 at wavelength λ3 to emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less.

The red coloring composition for a color filter of the present invention is a red coloring composition for a color filter containing a pigment (A), a pigment dispersant (B), and a binder resin (C). It contains at least three kinds of ketopyrrolopyrrole red pigments, anthraquinone red pigments, and benzimidazolone orange pigments. A target red color chromaticity can be achieved and a bright red filter segment can be formed.
In addition, by using the color filter of the present invention, it is possible to increase the brightness and contrast of the liquid crystal display device.

It is a schematic sectional drawing of a liquid crystal display device.

First, the red coloring composition for color filters of the present invention will be described. The red coloring composition for a color filter of the present invention contains a pigment (A), a pigment dispersant (B), and a binder resin (C), and if necessary, a photopolymerization initiator, a sensitizer, an organic Contains solvents and leveling agents.
The pigment constituting the red coloring composition for a color filter of the present invention includes at least three kinds of a diketopyrrolopyrrole red pigment, an anthraquinone red pigment, and a benzimidazolone orange pigment.
<Pigment (A)>

In the red coloring composition for a color filter of the present invention, at least three kinds of pigments are blended in order to achieve both high brightness and high contrast. In other words, the use of a diketopyrrolopyrrole red pigment, which is advantageous for improving brightness, does not provide sufficient contrast, and the film thickness increases, so anthraquinone, which is advantageous for high contrast and thin film formation. A red pigment is used in combination. However, when an anthraquinone red pigment is blended in order to obtain sufficient contrast, sufficient brightness cannot be obtained. In addition, when an anthraquinone red pigment is used in combination for the purpose of thinning the film, the target color is not obtained. Therefore, it is necessary to adjust the chromaticity with a pigment that is yellower than the diketopyrrolopyrrole red pigment.
Therefore, a benzimidazolone-based orange pigment that can provide sufficient brightness and is advantageous for thinning is blended.
In addition to the above three types of pigments, the red coloring composition for color filters of the present invention includes quinacridone-based, perylene-based, pyranthrone-based, azo-based red pigments, isoindoline-based, and quinophthalone for chromaticity adjustment. System, anthraquinone and other yellow pigments can be contained.

Examples of the diketopyrrolopyrrole red pigment include C.I. I. Pigment Orange 71, C.I. I. Pigment Red 254, 255, 264 and the like. Among them, C.I. I. Pigment Red 254 is particularly preferably used because of its excellent light resistance, heat resistance, transparency, and coloring power.
Examples of the anthraquinone red pigment include C.I. I. Pigment Red 177, and is preferably used because of its excellent light resistance, heat resistance, transparency, and coloring power.

  Examples of benzimidazolone orange pigments include C.I. I. Pigment Orange 36, 60, 62, 64, 72, and the like. Among them, C.I. I. Pigment Orange 64 is particularly preferably used because it is advantageous for thinning and brightness.

In the red coloring composition for a color filter of the present invention, the content of the three pigments is 30 to 85% by weight of a diketopyrrolopyrrole red pigment based on the total weight of the pigment (100% by weight), an anthraquinone type. It is preferably 10 to 60% by weight of red pigment, 5 to 30% by weight of benzimidazolone orange pigment, more preferably 35 to 65% by weight of diketopyrrolopyrrole red pigment, and 20 to 50% by weight of anthraquinone red pigment. %, Benzimidazolone-based orange pigment 5 to 25% by weight. When the content of the diketopyrrolopyrrole red pigment is less than 30% by weight, sufficient brightness cannot be obtained, and when it exceeds 85% by weight, sufficient contrast cannot be obtained. Further, when the content of the anthraquinone red pigment is less than 10% by weight, sufficient contrast cannot be obtained, and when it exceeds 60% by weight, sufficient brightness cannot be obtained. In addition, when the content of the benzimidazolone orange pigment is less than 5% by weight, a sufficient thinning effect does not appear, and when it exceeds 30% by weight, the heat resistance is poor and the brightness after manufacturing the color filter is low. It will go down.

The three kinds of pigments contained in the red coloring composition for a color filter of the present invention have an average primary particle diameter in the range of 10 to 50 nm in order to realize high brightness and high contrast of the color filter. Is preferred. The average primary particle diameter of the pigment can be measured by observation with a transmission electron microscope. When the average primary particle diameter of the three kinds of pigments is larger than 50 nm, the brightness and contrast of the color filter are low. When the average primary particle diameter is smaller than 10 nm, the pigment dispersion is very difficult, and the fluidity as the coloring composition is reduced. It becomes difficult to ensure. As a result, the brightness and contrast of the color filter tend to deteriorate.

As a means for reducing the primary particle size of the pigment, a method of mechanically pulverizing the pigment (referred to as a grinding method), a solution dissolved in a good solvent is introduced into a poor solvent, and a pigment having a desired primary particle size is precipitated. And a method of producing a pigment having a desired primary particle size at the time of synthesis (referred to as a synthetic precipitation method). Depending on the synthesis method and chemical properties of the pigment used, an appropriate method can be selected for each pigment. Each method will be described below.

In the grinding method, the pigment is mechanically kneaded with a grinding agent such as water-soluble inorganic salt such as salt and a water-soluble organic solvent that does not dissolve it using a ball mill, sand mill, or kneader (hereinafter, this process is salted). In this method, the inorganic salt and the organic solvent are washed away with water and dried to obtain a pigment having a desired specific surface area. However, since the pigment may crystallize due to the salt milling treatment, a method of preventing crystal growth by adding a solid resin that is at least partially dissolved in the water-soluble organic solvent or a dispersion aid described later during the treatment is effective. It is.
As for the ratio of the pigment to the inorganic salt, if the ratio of the inorganic salt is increased, the efficiency of refining the pigment is improved, but the productivity is lowered because the amount of pigment processed is reduced. In general, the inorganic salt is used in an amount of 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 1 part by weight of the pigment.

Further, the water-soluble organic solvent is added so that the pigment and the inorganic salt are uniformly solidified. Depending on the blending ratio of the pigment and the inorganic salt, an amount of 50 to 300% by weight of the pigment is usually used. It is done.
The grinding method will be explained in more detail. A small amount of a water-soluble organic solvent is added as a wetting agent to a mixture of a pigment and a water-soluble inorganic salt, and after kneading with a kneader or the like, the mixture is put into water and high-speed. Agitate with a mixer to make a slurry. Next, a pigment having a desired primary particle size can be obtained by filtering, washing, and drying the slurry.

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 size. The primary method depends on the type and amount of the solvent, the precipitation temperature, the precipitation rate, etc. The particle size can be controlled. In general, pigments are difficult to dissolve in a solvent, so the solvents that can be used are limited. For example, strongly acidic solvents such as concentrated sulfuric acid, polyphosphoric acid, and chlorosulfonic acid, or bases such as dimethylformamide solution of liquid ammonia and sodium methylate 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, a method of injecting a sulfuric acid solution into water is generally used from the viewpoint of cost. The sulfuric acid concentration is not particularly limited, but is preferably 95 to 100% by weight. The amount of sulfuric acid used with respect to the pigment is not particularly limited. However, if the amount is too small, the solution viscosity is high and handling becomes poor. On the other hand, if the amount is too large, the pigment processing efficiency decreases. Is preferably used. The pigment need not be completely dissolved. The temperature at the time of dissolution is preferably from 0 to 50 ° C. Below this temperature, sulfuric acid may freeze and the solubility will be low. If the temperature is too high, side reactions tend to occur. The temperature of the water to be injected is preferably 1 to 60 ° C., and if the injection is started at a temperature higher than this temperature, it boils with the heat of dissolution of sulfuric acid, which is dangerous. It will freeze at temperatures below this. The injection time is preferably 0.1 to 30 minutes with respect to 1 part of the pigment.

The primary particle size of the pigment can be controlled while taking into consideration the degree of sizing of the pigment by selecting a method that combines a precipitation method such as the acid pasting method and a grinding method such as the 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, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant described later can be used in combination in order to prevent pigment aggregation associated with primary particle size control. In addition, by controlling the primary particle size in the form of coexistence of two or more pigments, even a pigment that 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 depositing a pigment having a desired primary particle size. However, when the produced fine pigment is taken out from the solvent, if the pigment particles are not aggregated into large secondary particles, filtration, which is a general separation method, becomes difficult. It is applied to azo pigments that are easily synthesized in water.
Furthermore, as a means for controlling 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 in which the pigment is dry-pulverized). It is also possible.

<Pigment dispersant (B)>
In the present application, when dispersing the colorant in the colorant carrier, a pigment dispersant such as a dye derivative, a resin-type dispersant, or a surfactant is appropriately contained. Since the pigment dispersant has a great effect of preventing re-aggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using a dispersion aid has spectral characteristics and viscosity stability. Will be better.

(Dye derivative)
Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The blending amount of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving the dispersibility of the added colorant. It is. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by weight or less, more preferably 35 parts by weight or less with respect to 100 parts by weight of the colorant.

(Resin type dispersant)
The resin-type dispersant has a colorant affinity part that has the property of adsorbing to the added colorant, and a part that is compatible with the colorant carrier, and adsorbs to the added colorant to disperse in the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

Among the above-mentioned dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion is lowered and a high contrast is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer or side chain is preferable. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles and the like are preferred.
The resin-type dispersant is preferably used in an amount of about 5 to 200% by weight relative to the total amount of the pigment, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

  Commercially available resin-type dispersants include Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., Ciba Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 755 , 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

The amount of the resin-type dispersant and the surfactant added is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is adversely affected by the excessive dispersant. May affect.
<Binder resin (C)>
The binder resin disperses, dyes, or penetrates the colorant, and examples thereof include a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. 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, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  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 region of 400 to 700 nm in the visible light region.

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

  When the binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin is preferably used in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

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

Examples of the vinyl alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, 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 of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

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

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to 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 a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

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

  Examples of unsaturated ethylenic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

[Thermosetting compound]
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin which is a binder resin.

  Examples of the thermosetting compound include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, phenol compounds and / or resins, but the present invention is not limited thereto.

(Organic solvent)
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated in the coloring agent carrier, and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easy to form, it is preferable to contain an organic solvent. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include 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 Dimonomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene Glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl 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, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, Acetic acid Propyl, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl 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 can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a desired colored film having a uniform thickness. Is preferred.

<Photopolymerizable monomer (D)>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 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 ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether 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 Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

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

<Photopolymerization initiator (E)>
The photopolymerization initiator used in the present invention is a compound that generates active species capable of initiating polymerization of the photopolymerizable monomer by exposure to radiation such as ultraviolet rays, visible rays, far ultraviolet rays, electron beams, and X-rays. is there.

Examples of such a photopolymerization initiator include 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) Acetophenone series such as methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Compound: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin iso Benzoin compounds such as propyl ether or benzyl dimethyl 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 diethyl thioxanthone; 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, Triazine compounds such as 4-trichloromethyl- (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-ben) Oxime)], or 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 trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

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

(Sensitizer)
Furthermore, the sensitizer can be contained in the pigment composition of the present invention.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

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

(Antioxidant)
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. In addition, the antioxidant used in the present invention preferably does not contain a halogen atom.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 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- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2'-thio- Su- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2′thiodiethylbis- (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-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro Cinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include 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-butanetetracarboxylate, 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 oligomer type having a hindered amine structure And poly Mer type compounds can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl 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, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (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 (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 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 and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

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

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2- 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.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester 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 singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the red coloring composition because the spectral characteristics and sensitivity are good.

(Amine compounds)
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

(Leveling agent)
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in 100% by weight of the total weight 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, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

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

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

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

(Curing agent, curing accelerator)
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), 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 (for example tri Phenylphosphine ), Guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino) -S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can do. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

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

(Storage stabilizer)
Examples of the storage stabilizer include organic acids such as lactic acid and oxalic acid and methyl ether thereof, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

(Adhesion improver)
Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include 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 weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight 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 the polyfunctional thiol.
By using a polyfunctional thiol together with a photopolymerization initiator, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation, so the resulting colored composition is highly sensitive. It becomes. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable. Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibu 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 individually by 1 type or in mixture of 2 or more types.
The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the colorant. If the polyfunctional thiol content is less than 0.05 parts by weight, the effect of the chain transfer agent is small. .

(Method for producing red coloring composition)
The red coloring composition of the present invention comprises a kneader containing the azo pigment [A] represented by the general formula (1) in a colorant carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid. It can be manufactured by finely dispersing (colorant dispersion) using various dispersing means such as a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.
When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Removal of coarse particles)
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

(Color filter)
The color filter for a liquid crystal display device of the present invention will be described.
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, and the at least one red filter segment is made of the red coloring composition of the present invention. Preferably there is.
Moreover, the green coloring composition which forms a green filter segment can be produced similarly to the above-mentioned red coloring composition by replacing with a green pigment or dye. The same applies to the blue coloring composition forming the blue filter segment.

  The green filter segment can be formed using a normal green coloring composition. Examples of the green coloring composition include C.I. I. It is a composition obtained by using a green pigment such as CI Pigment Green 7, 10, 36, 37, or 58. Green coloring compositions include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213, or a yellow pigment 214 and the like can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 or the like is used.

  In addition, C.I. I. Purple pigments such as CI Pigment Violet 23, C.I. I. A metal lake pigment of a rhodamine dye such as CI Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5 can be used in combination. Further, a basic dye or a salt forming compound of an acidic dye that exhibits blue or purple can be used.

  As the substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

(Color filter manufacturing method)
The color filter of the present invention can be produced by using a coloring composition by a printing method or a photolithography method.

  Formation of a colored film by a printing method can be performed by simply repeating printing and drying of a colored composition prepared as a printing ink, so that the color filter manufacturing method is low cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming a colored film by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

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

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for manufacturing a color filter by using a transparent conductive film formed on a substrate and forming a colored film on the transparent conductive film by electrodeposition of colloidal particles. . The transfer method is a method in which a colored film is formed in advance on the surface of a peelable transfer base sheet, and this colored film is transferred to a desired substrate.

If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the panel can be increased and the luminance can be improved.
On the color filter of the present invention, an overcoat film or a transparent conductive film is formed as necessary.
(Liquid crystal display device)
A liquid crystal display device provided with the color filter of the present invention will be described.

  The liquid crystal display device of the present invention includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED. In the present invention, it is preferable to use a white LED in that the red reproduction region is widened. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 provided with a color filter of the present invention. The apparatus 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 that are arranged to face each other, and a liquid crystal LC is sealed between them.

  The liquid crystal LC is aligned according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence). A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

  On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

  A transparent protective film (not shown) is formed so as to cover the color filter 22 and further, a transparent electrode layer 23 made of, for example, ITO is formed thereon, and the alignment layer 24 covers the transparent electrode layer 23. Is provided.

  A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. A backlight unit 30 is provided below the polarizing plate 15.

  White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED, and those in which a phosphor is contained in a resin package of a blue LED. The wavelength (maximum emission intensity within a range of 430 nm to 485 nm ( λ3), a wavelength (λ4) at which the emission intensity is maximum within a range of 530 nm to 580 nm, a wavelength (λ5) at which the emission intensity is maximum within a range of 600 nm to 650 nm, and a wavelength The ratio (I4 / I3) of the emission intensity I3 at λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5 / I3 ) Is a white LED light source (LED1) having a spectral characteristic of 0.1 or more and 1.3 or less, or has a wavelength (λ1) with a maximum emission intensity in the range of 430 nm to 485 nm. The second emission intensity peak wavelength (λ2) is in the range of 530 nm to 580 nm, and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ1 to the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0. A white LED light source (LED2) having a spectral characteristic of 0.7 or less is preferred.

  Specific examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation), NSSW304D-HG-V1 (manufactured by Nichia Corporation), and the like.

Specific examples of the LED 2 include NSSW 440 (manufactured by Nichia Corporation), NSSW304D (manufactured by Nichia Corporation), and the like.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  Moreover, the measuring method of the average primary particle diameter of a pigment, the weight average molecular weight (Mw) of resin, and the measuring method of the acid value of resin are as follows.

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

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw).

(Resin acid value)
To 0.5 to 1.0 part of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L KOH aqueous solution is used as a titrant and an automatic titrator (“COM-555”). Titration using Hiranuma Sangyo) and the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20 mass%. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the obtained copolymer solution, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz, Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Manufacture of colorants>
(Red colorant (PR-1))
Commercially available C.I. I. 100 parts of Pigment Red 254 (PR254) ("Irgafore Red B-CF" (diketopyrrolopyrrole red pigment) manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol, 1 gallon kneader (Inoue Seisakusho Co., Ltd.) And kneaded at 60 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red colorant (PR-1) were obtained. The average primary particle size was 33 nm.

(Red colorant (PR-2))
Red pigment C.I. I. Pigment Red 264 pigment (“IRGAZIN DPP RUBINE TR” (diketopyrrolopyrrole red pigment) manufactured by BASF Japan Ltd.), 1600 parts of sodium chloride, and 190 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), 1 gallon made of stainless steel The mixture was charged into a kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, It dried at 80 degreeC for 24 hours, and obtained 156 parts of red coloring agents (PR-2). The average primary particle size was 38 nm.

(Red colorant (PR-3))
C. I. Pigment Red 254, C.I. I. Pigment Red 177 (PR177) (“chromophthal red A2B” manufactured by BASF (anthraquinone red pigment)) was used in the same manner as in the production of the red colorant (PR-29). 3) 97 parts were obtained. The average primary particle size was 28 nm.

(Red colorant (PR-4))
C. I. Pigment Red 254, C.I. I. Pigment Red 179 (PR179) ("Pariogen Maroon L-3920" (perylene red pigment) manufactured by BASF) was used in the same manner as in the production of the red colorant (PR-29), and the red colorant (PR -4) 97 parts were obtained. The average primary particle size was 41 nm.

(Red colorant (PR-5))
C. I. Pigment Red 254, C.I. I. Pigment Red 242 (PR242) (Clariant's Sandorin Scallet 4RF (disazo red pigment)) was used in the same manner as in the production of the red colorant (PR-29), and 97 parts of the red colorant (PR-5) Got. The average primary particle size was 39 nm.

(Red colorant (PR-6))
C. I. Pigment Red 254, C.I. I. Pigment Red 176 (PR176) (Clariant's “Novoperm Carmine HF3C” (benzimidazolone red pigment) was used in the same manner as in the production of the red colorant (PR-29). 6) 97 parts were obtained, and the average primary particle size was 35 nm.

(Orange colorant (PO-1))
Commercially available C.I. I. Pigment Orange 36 (PO36) (Clariant's “Novoperm Orange HL 70-EDS VP 3065” (benzimidazolone-based orange pigment)) 100 parts, sodium chloride 1200 parts, and diethylene glycol 120 parts 1 gallon kneader (Inoue Seisakusho) And kneaded at 60 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of an orange colorant (PO-1) were obtained. The average primary particle size was 39 nm.

(Orange colorant (PO-2))
C. I. Pigment Orange 36, C.I. I. Pigment Orange 64 (PO64) (“Cromophtal Orange K 2960” (benzimidazolone-based orange pigment) manufactured by BASF Corporation) was used in the same manner as in the production of the orange colorant (PO-1). PO-2) was obtained. The average primary particle size was 38 nm.

(Orange colorant (PO-3))
C. I. Pigment Orange 36 is a commercially available C.I. I. Except having changed to pigment orange 43 (PO43) ("HOSTPERM ORANGE GR" by Clariant), it carried out similarly to manufacture of an orange coloring agent (PO-1), and obtained the orange coloring agent (PO-3). The average primary particle size was 42 nm.

(Yellow colorant (PY-1))
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY-1) was obtained. The average primary particle size was 36 nm.

(Yellow colorant (PY-2))
C. I. 100 parts of Pigment Yellow 138 (PY138) (“Pariotor Yellow K0960-HD” manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. for 6 hours. Kneaded. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A colorant (PY-2) was obtained. The average primary particle size was 40 nm.

(Green colorant (PG-1))
Phthalocyanine green pigment C.I. I. Pigment Green 7 (PG7) (“Rionol Green YS-07” manufactured by Toyocolor Co., Ltd.) 200 parts, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 120 ° C. Kneaded for 4 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. And 490 parts of a green colorant (PG-1) was obtained. The average primary particle size was 50 nm.

(Blue colorant (PB-1))
C. I. 100 parts of Pigment Blue 15: 6 (PB15: 6) (“Rionol Blue ES” manufactured by Toyocolor Co., Ltd.), 800 parts of crushed salt, and 100 parts of diethylene glycol were charged in a stainless 1 gallon kneader (Inoue Seisakusho), 70 The mixture was kneaded for 12 hours. The mixture was poured into 3000 parts of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 98 parts of blue A colorant (PB-1) was obtained. The average primary particle size was 28 nm.

(Purple colorant (PV-1))
C. I. 120 parts of Pigment Violet 23 (PV23) (“Fast Violet RL” manufactured by Clariant), 1600 parts of crushed salt, and 100 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. . The mixture was poured into 5000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 118 parts of purple A colorant (PV-1) was obtained. The average primary particle size was 26 nm.

<Method for producing colorant dispersion>
(Colorant dispersion (DR-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colorant dispersion (DR-1) was produced by filtration using a filter.

Red colorant (PR-1): 12.0 parts Resin type dispersant: 1.0 part ("EFKA4300" manufactured by BASF)
Acrylic resin solution 1: 35.0 parts Solvent: 52.0 parts Propylene glycol monomethyl ether acetate (PGMAC)

(Colorant dispersion (DR-2 to 6, DY-1 to 2, DO-1 to 3, DG-1, DB-1, DV-1)
The colored compositions (DR-2 to 6) (DY-1 to 2) and (D) are the same as the colorant dispersion (DR-1) except that the mixture is changed to the mixture (parts by weight) shown in Table 1. DO-1 to 3), (DG-1), (DB-1), and (DV-1) were produced.

  In Table 1, EFKA4300, BYK-LPN6919, and PGMAC are as follows. EFKA4300: manufactured by BASF; BYK-LPN6919: manufactured by Big Chemie; PGMAC: propylene glycol monomethyl ether acetate

<Method for producing photosensitive green coloring composition and photosensitive blue coloring composition>
(Photosensitive green coloring composition (RG-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive green coloring composition (RG-1).

Colorant dispersion (DG-1): 45.1 parts (CI Pigment Green 7 (PG7))
Colorant dispersion (DY-2): 21.6 parts (CI Pigment Yellow 138 (PY138))
Acrylic resin solution 2: 4.3 parts Photopolymerizable monomer: 4.2 parts (“Aronix M402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 1.2 parts ("Irgacure 907" manufactured by BASF)
Sensitizer: 0.4 parts (“DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Solvent: 23.2 parts (propylene glycol monomethyl ether acetate (PGMAC))

(Photosensitive blue coloring composition (RB-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive blue colored composition (RB-1).

Colorant dispersion (DB-1): 24.6 parts (CI Pigment Blue 15: 6 (PB15: 6))
Colorant dispersion (DV-1): 12.9 parts (CI Pigment Violet 23 (PV23))
Acrylic resin solution 2: 23.0 parts Photopolymerizable monomer: 2.1 parts (“Aronix M402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 0.6 part ("Irgacure 907" manufactured by BASF)
Sensitizer: 0.2 part (“DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Solvent: 36.6 parts (propylene glycol monomethyl ether acetate (PGMAC))

<Preparation of red coloring composition>
[Example 1]
(Photosensitive red coloring composition (RR-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (RR-1).

Colorant dispersion (DR-1): 51.3 parts (CI Pigment Red 254 (PR254))
Colorant dispersion (DR-2): 8.1 parts (CI Pigment Red 177 (PR177))
Colorant dispersion (DO-1): 7.3 parts (CI Pigment Orange 36 (PO36)
Acrylic resin solution 2: 4.3 parts Photopolymerizable monomer: 4.2 parts (“Aronix M402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 1.2 parts (“OXE-02” manufactured by BASF)
Sensitizer: 0.4 parts (“DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Solvent: 23.2 parts (propylene glycol monomethyl ether acetate (PGMAC))

[Examples 2 to 11 and Comparative Examples 1 to 10]
(Photosensitive coloring composition (RR-2-23)
Hereinafter, the color composition, the acrylic resin solution, the photopolymerizable monomer, the photopolymerization initiator, the sensitizer, and the solvent are photosensitive except that they are changed to the types shown in Tables 2 and 3 and the blending amount (parts by weight). In the same manner as the red coloring composition (RR-1), photosensitive red coloring compositions (RR-2 to 23) were produced. Moreover, “Aronix M402” manufactured by Toa Gosei Co., Ltd. was used as the photopolymerizable monomer described in Tables 7 to 9, and “DETX-S” manufactured by Nippon Kayaku Co., Ltd. was used as the sensitizer.

[Evaluation of photosensitive red coloring composition]
The color characteristics and film thickness of the photosensitive red coloring compositions obtained in Examples and Comparative Examples were evaluated by the following methods. Tables 4 and 5 show the evaluation results.

<Formation of filter segment>
A black matrix is patterned on a glass substrate, and the light source NSSW306D-HG-V1 (manufactured by Nichia Corporation, LED-1) is used as a light source by using the colored compositions shown in Tables 2 and 3 on the substrate with a spin coater. ) Or LED light source NSSW440 (manufactured by Nichia Chemical Co., Ltd., LED-2), coatings were formed to film thicknesses having values of x and y shown in Tables 4 and 5, respectively, to form a coating film of a colored composition. The film was irradiated with ultraviolet rays of 150 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, an alkali developer composed of 0.1% by weight of sodium carbonate 0.15% by weight sodium hydrogen carbonate 0.05% by weight anionic surfactant (“PERILEX NBL” manufactured by Kao Corporation) and 99.7% by weight of water After removing the unexposed portion by spray development, the substrate was washed with ion-exchanged water, and this substrate was heated at 230 ° C. for 20 minutes to form red filter segments shown in Tables 10 and 11.

<Evaluation of color characteristics and film thickness>
For the obtained red filter segment, LED light source NSSW306D-HG-V1 (manufactured by Nichia Corporation, LED-1) or LED light source NSSW440 (manufactured by Nichia Corporation, LED-2) is used as a light source as necessary. The color characteristics (x, y, Y) of the red filter segment when irradiated with light were measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.).
The film thickness was measured using a surface shape measuring device DEKTAK150 (manufactured by ULVAC-ES).
<Contrast ratio>

The obtained photosensitive red coloring composition was subjected to a microspectrophotometer (Olympus) after heat treatment at 230 ° C. on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater and changing the number of rotations. It applied so that the x value in LED-1 or LED-2 measured using “OSP-SP100” manufactured by Optics Co., Ltd. would be three substrates with the x values in Tables 4 and 5 sandwiched between the respective light sources. Next, the film was dried at 70 ° C. for 20 minutes, exposed to ultraviolet light with an integrated light amount of 150 mJ / cm ² using an ultrahigh pressure mercury lamp, and developed with an alkaline developer at 23 ° C. to obtain a coated substrate. Next, after heating at 230 ° C. for 60 minutes and allowing to cool, the x value and contrast ratio of each of the obtained coated substrates were measured, and the contrast at the x values in Tables 4 and 5 was determined from the three-point data by the primary correlation method. It was.

In the red coloring composition for a color filter containing the pigment (A) of the present invention, a pigment dispersant (B), and a binder resin (C), the pigment is a diketopyrrolopyrrole red pigment, an anthraquinone type The red photosensitive coloring composition for a color filter, which contains at least three kinds of a red pigment and a benzimidazolone orange pigment, has a film thickness higher than that of the comparative example while the filter segment exhibits high brightness Y. It was found that the thickness was reduced to 0.1 μm or more, and a high value could be maintained even in the contrast ratio.

<Production of color filter and liquid crystal surface device>
[Example 14]
(Color filter (CF-1))
A red filter segment formed using the photosensitive red coloring composition (RR-1) by the same method as the red filter segment of Example 1, and an LED light source NSSW306D-HG-V1 (manufactured by Nichia Corporation, LED) -1), the green filter segment is adjusted to the chromaticity of xx = 0.265, y = 0.690 using the photosensitive green coloring composition (RG-1), and the blue filter segment is photosensitive. Was applied to the chromaticity of x = 0.150 and y = 0.060 using the luminescent blue coloring composition (RB-1) to obtain a color filter (CF-1).

[Example 15, Comparative Example 10]
(Color filter (CF-2 to 3))
In the same manner as in Example 14 (color filter (CF-1)) except that the photosensitive red coloring composition described in Table 9 was used instead of the photosensitive red coloring composition (RR-1), Color filters (CF-2 to 3) were obtained.

<Evaluation of color filter>
The color characteristic of the color filter when the color filter produced in the example and the comparative example is irradiated with light using the LED light source NSSW306D-HG-V1 (manufactured by Nichia Corporation, LED-1) as the light source is a microspectrophotometer. (Olympus Optical Co., Ltd. “OSP-SP100”). Chromaticity point (x, y) in the CIE color system of each color filter segment, NTSC ratio (standard primary three colors defined by the US National Television System Committee (NTSC), red (0.67, 0.33), Table 6 shows the brightness (Y value) of white display and the ratio of the area surrounded by green (0.21, 0.71) and blue (0.14, 0.08).

  The color filter coloring composition formed from the red coloring composition of the present invention has a wide color reproduction of NTSC ratio of 96% while maintaining a high white display brightness while maintaining a high white display brightness. It was confirmed that it showed sex.

Claims (8)

  In the red coloring composition for a color filter containing a pigment (A), a pigment dispersant (B), and a binder resin (C), the pigment (A) is a diketopyrrolopyrrole red pigment, anthraquinone A red coloring composition for a color filter, comprising: a red pigment and a benzimidazolone orange pigment.   The content of the three pigments is 30 to 85% by weight of a diketopyrrolopyrrole red pigment, 10 to 60% by weight of an anthraquinone red pigment, and 5 to 30 of a benzimidazolone orange pigment based on the total weight of the pigment. The red coloring composition for a color filter according to claim 1, wherein the red coloring composition is used by weight.   The anthraquinone red pigment is C.I. I. Pigment Red 177, and the benzimidazolone orange pigment is C.I. I. It is Pigment Orange 64, The red coloring composition for color filters of Claim 1 or 2 characterized by the above-mentioned. The red colored composition for a color filter according to any one of claims 1 to 3, further comprising a photopolymerizable monomer (D) and a photopolymerization initiator (E). A color filter comprising a red filter segment formed using the red coloring composition for a color filter according to claim 1. A liquid crystal display device comprising the color filter according to claim 5. The liquid crystal display device has a backlight,
The backlight has a wavelength (λ1) at which the emission intensity is maximum within a range of 430 nm to 485 nm, a peak wavelength (λ2) of a second emission intensity within a range of 530 nm to 580 nm, and a wavelength at λ1 7. A liquid crystal display device according to claim 6, wherein the liquid crystal display device is a white LED light source having spectral characteristics in which the ratio (I2 / I1) of the emission intensity I1 to the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less. . The liquid crystal display device according to claim 6 has a backlight,
The backlight has a wavelength (λ3) where the emission intensity becomes maximum within a range of 430 nm to 485 nm, has a wavelength (λ4) where the emission intensity becomes maximum within a range of 530 nm to 580 nm, and has a wavelength of 600 nm to 650 nm. A wavelength (λ5) at which the emission intensity becomes maximum within the range, and the ratio (I4 / I3) of the emission intensity I3 at the wavelength λ3 and the emission intensity I4 at the wavelength λ4 is 0.2 or more and 0.4 or less, 7. The white LED light source having a spectral characteristic in which a ratio (I5 / I3) of the emission intensity I3 at the wavelength λ3 and the emission intensity I5 at the wavelength λ5 is 0.1 or more and 1.3 or less. Liquid crystal display device.