JP2010091886A - Red-colored composition for color filter and color filter using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a red-colored composition for color filters, which is excellent in dispersibility and fluidity and suppresses crystal deposition in a filter segment production process to thereby enable a color filter having a high contrast ratio and high lightness to be manufactured. <P>SOLUTION: The red-colored composition for color filters includes: a pigment carrier comprising a resin, a precursor thereof or a mixture of these; a diketopyrrolopyrrole red pigment; a diketopyrrolopyrrole dye derivative; a thiazine indigo dye derivative; and, optionally, an active energy ray-curable monomer and a photopolymerization initiator. A color filter with a red filter segment formed from the red-colored composition for color filters is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

In recent years, liquid crystal display devices have been evaluated for space saving, light weight, power saving, and the like due to their thinness, and recently they have been rapidly spread to television applications. For television applications, it is required to further improve performance such as luminance and contrast, and further enhancement of brightness and contrast is desired for color filters that are members of liquid crystal display devices.
Conventionally, the red filter segment constituting the color filter includes C.I., which is an anthraquinone pigment. I. Pigment Red 177 has been used. This pigment can be easily miniaturized by a mechanical treatment, and the finer pigment can be dispersed relatively easily, which is useful for increasing the contrast (for example, Patent Documents). 1). However, there is a limit to the brightness improvement in terms of spectral characteristics.

Recently, in place of anthraquinone red pigment, C.I. is a diketopyrrolopyrrole red pigment. I. Pigment Red 254 is often used. This pigment is C.I. I. The transmission spectrum near 600 nm is closer to the short wavelength side than Pigment Red 177, and the absorption of the red bright line of the backlight is less, so the transparency is high and the brightness can be improved (for example, Patent Documents 2 and 3). reference).
However, the diketopyrrolopyrrole red pigment is easy to be miniaturized by mechanical treatment, but has a strong cohesive force. Therefore, as the degree of miniaturization progresses, a heat of 100 to 280 ° C. is usually applied in the filter segment manufacturing process. There is a problem that crystal deposition occurs on the surface of the coating film in the curing process or in the ITO film forming process exposed to 200 ° C. or higher. This may cause a decrease in contrast and may scatter to surrounding filter segments and stain the color.

In order to solve such problems, organic pigments other than diketopyrrolopyrrole such as benzidine yellow and 4,4′-diamino-1,1′-bianthraquinone as crystal growth inhibitors of diketopyrrolopyrrole pigments A method of blending a sulfonic acid derivative, or a method of blending a dispersant having a specific structural site has been proposed (see Patent Documents 4 and 5). Moreover, paying attention to the X-ray diffraction pattern of the diketopyrrolopyrrole pigment, a method for suppressing crystal precipitation by limiting the half width to a certain range has been proposed (see Patent Document 6). However, the diketopyrrolopyrrole pigment has been further refined to meet the recent demand for higher contrast, and it is difficult to completely suppress crystal precipitation with the above-described derivatives.
Japanese Patent Laid-Open No. 10-148712 Japanese Patent Laid-Open No. 11-231516 JP 2002-328217 A JP 2001-240780 A JP 2008-69244 A JP 2002-240780 A

  The present invention is excellent in dispersibility and fluidity, and further suppresses crystal precipitation in the filter segment preparation step, whereby a color filter having a high contrast ratio and high brightness can be produced. And a color filter using the same.

The present inventors have found that the above problem can be solved by using a specific diketopyrrolopyrrole dye derivative and a thiazineindigo dye derivative in combination with a diketopyrrolopyrrole red pigment.
That is, the present invention relates to a pigment carrier comprising a resin, a precursor thereof or a mixture thereof, a diketopyrrolopyrrole red pigment, a diketopyrrolopyrrole dye derivative represented by the following general formula (1), and the following general formula ( The present invention relates to a red coloring composition for a color filter comprising the thiazine indigo dye derivative represented by 2).

式（１）において、Ｒ₁〜Ｒ₁₀は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、シアノ基、スルホニル基、カルボキシル基、ジアルキルアミノ基、ハロゲノアルキル基、アルコキシカルボニル基、アルキルメルカプト基、カルバモイル基、またはスルファモイル基を表し、Ｒ₁〜Ｒ₁₀の少なくとも１つはＥの結合手である。ｐは、１〜４の整数を表す。式（２）において、Ｒ₁₁及びＲ₁₂は、それぞれ独立に、−（Ｅ）_ｑ基以外の置換基を有していてもよい、芳香族または脂肪族炭素環または複素環を形成するために必要な基を表す。式（１）及び式（２）において、Ｅは、独立に、下記一般式（３）または下記一般式（４）を表す。ｑは、１〜６の整数を表す。

In Formula (1), R _{1 to} R ₁₀ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group, a sulfonyl group, a carboxyl group, a dialkylamino group, a halogenoalkyl group, an alkoxycarbonyl group, Represents an alkylmercapto group, a carbamoyl group, or a sulfamoyl group, and at least one of R _{1 to} R ₁₀ is a bond of E; p represents an integer of 1 to 4. In formula (2), R ₁₁ and R ₁₂ each independently form an aromatic or aliphatic carbocycle or heterocycle which may have a substituent other _than- (E) _q group. Represents the necessary group. In formula (1) and formula (2), E independently represents the following general formula (3) or the following general formula (4). q represents the integer of 1-6.

式（３）において、Ｒ₁₃及びＲ₁₄は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０のアルキル基または置換基を有していてもよい炭素数２〜３０のアルケニル基を表し、Ｒ₁₃及びＲ₁₄は窒素、酸素または硫黄原子を含む置換されてもよい複素環を形成していてもよい。Ｘは、−Ｓ−、−Ｏ−、−ＳＯ₂−、−ＣＯ−、−ＳＯ₂ＮＲ−、−ＮＲＳＯ_２−、−ＣＯＮＲ−、−ＣＨ₂ＮＲＣＯＣＨ₂ＮＲ−または−（ＣＨ₂）_ｍＮＨ−を表す（但し、ｍは、１〜１０の整数を表す。Ｒは、独立に、水素原子、置換基を有していてもよい炭素数１〜２０のアルキル基、置換基を有していてもよい炭素数２〜２０のアルケニル基または置換基を有していてもよい炭素数６〜２０のアリール基を表す）。ａは、０または１を表す。Ｙは、置換基を有していてもよい炭素数１〜２０のアルキレン基、置換基を有していてもよい炭素数２〜２０のアルケニレン基、置換基を有していてもよい炭素数６〜２０のアリーレン基または窒素、酸素または硫黄原子を含む置換されていてもよい複素環を表す（これらの基は、二つ以上組合せてもよく、−ＮＲ−、−Ｏ−、−ＳＯ₂−、−ＣＯ−または−ＣＯＮＨ−から選ばれる２価の連結基で互いに結合していてもよい。ここで、Ｒは上記定義の通りである。）。ｂは、０または１を表す。式（４）において、Ｒ₁₅〜Ｒ₁₈は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１〜２０のアルキル基、置換基を有していてもよい炭素数２〜２０のアルケニル基または置換基を有していてもよい炭素数６〜２０のアリール基を表す。Ｒ₁₉は、水素原子、置換基を有していてもよい炭素数１〜２０のアルキル基または置換基を有していてもよい炭素数２〜２０のアルケニル基を表す。Ｚは、−ＣＨ_２ＮＲ’ＣＯＣＨ_２ＮＲ’−、−ＣＨ_２ＮＲ’ＣＯＣＨ_２ＮＲ’−Ｇ−、−ＮＲ’−、−ＮＲ’−Ｇ−ＣＯ−、−ＮＲ’−Ｇ−ＣＯＮＲ’−、−ＮＲ’−Ｇ−ＳＯ_２−、−ＮＲ’−Ｇ−ＳＯ_２ＮＲ’−、−Ｏ−Ｇ−ＣＯ−、−Ｏ−Ｇ−ＣＯＮＲ’−、−ＳＯ_２−、−Ｏ−Ｇ−ＳＯ_２−、または−Ｏ−Ｇ−ＳＯ_２ＮＲ’−を表す(Ｇは、置換基を有していてもよい炭素数１〜２０のアルキレン基、置換基を有していてもよい炭素数２〜２０のアルケニレン基または置換基を有していてもよい炭素数６〜２０のアリーレン基を表し、Ｒ’は、水素原子、置換基を有していてもよい炭素数１〜２０のアルキル基、置換基を有していてもよい炭素数２〜２０のアルケニル基または置換基を有していてもよい炭素数６〜２０のアリール基を表す。)。ｃは、０または１を表す。

In Formula (3), R ₁₃ and R ₁₄ are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent or an alkyl group having 2 to 30 carbon atoms which may have a substituent. Represents an alkenyl group, and R ₁₃ and R ₁₄ may form an optionally substituted heterocyclic ring containing a nitrogen, oxygen or sulfur atom. X is, -S -, - O -, - SO 2 -, - CO -, - SO 2 NR -, - NRSO 2 -, - CONR -, - CH 2 NRCOCH 2 NR- , or - (CH _{2) m} NH -(Wherein m represents an integer of 1 to 10. R independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent). a represents 0 or 1; Y is an optionally substituted alkylene group having 1 to 20 carbon atoms, an optionally substituted alkenylene group having 2 to 20 carbon atoms, and an optionally substituted carbon number. 6-20 arylene group or a nitrogen, oxygen or (these groups representing a heterocyclic ring which may be substituted containing a sulfur atom may be combined two or more, -NR -, - O -, - SO 2 And may be bonded to each other through a divalent linking group selected from-, -CO- and -CONH-, wherein R is as defined above. b represents 0 or 1. In the formula (4), R _{15 to} R ₁₈ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon number 2. Represents an aryl group having 6 to 20 carbon atoms which may have -20 alkenyl groups or substituents; R ₁₉ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted alkenyl group having 2 to 20 carbon atoms. Z _{is, -CH 2 NR'COCH 2 NR '-} , - CH 2 NR'COCH 2 NR'-G -, - NR' -, - NR'-G-CO -, - NR'-G-CONR'- _{, -NR'-G-SO 2 -} , - NR'-G-SO 2 NR '-, - O-G-CO -, - O-G-CONR' -, - SO 2 -, - O-G- Represents SO ₂ — or —O—G—SO ₂ NR′— (G represents an optionally substituted alkylene group having 1 to 20 carbon atoms and optionally substituted carbon atoms. Represents a 2-20 alkenylene group or an arylene group having 6 to 20 carbon atoms which may have a substituent, and R ′ represents a hydrogen atom or an alkyl having 1 to 20 carbon atoms which may have a substituent. Group, an alkenyl group having 2 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 20 carbon atoms which may have a substituent. c represents 0 or 1;

The red coloring composition for a color filter of the present invention can further contain an active energy ray-curable monomer and a photopolymerization initiator.
In the red coloring composition for a color filter of the present invention, the total content of the diketopyrrolopyrrole pigment derivative and the thiazineindigo pigment derivative is 15% by weight to 40% by weight of the pigment. Is preferred.
Moreover, it is preferable that content of the said diketopyrrolopyrrole type pigment derivative is 2 to 10 weight% of the weight of a pigment.
Furthermore, this invention relates to the color filter characterized by including the red filter segment formed from the said red coloring composition for color filters.

  The red coloring composition for a color filter of the present invention is excellent in dispersibility and fluidity, and can further suppress crystal precipitation in the filter segment preparation step. Therefore, a color filter having a high contrast ratio and a high brightness can be provided by using the red coloring composition for a color filter of the present invention.

Hereinafter, embodiments of the present invention will be described.
First, various components of the red coloring composition for a color filter of the present invention will be described.
[Pigment]
The red coloring composition for a color filter of the present invention contains a diketopyrrolopyrrole red pigment. As a representative example, C.I. I. Pigment Red 254, 255, 264, 272 and the like. Among them, C.I. I. Pigment Red 254 is suitable because it has the highest transparency when reproducing red chromaticity conforming to the EBU standard, which is one of the television broadcasting standards, in combination with the red bright line of the three-wavelength cold cathode tube backlight. It is.
In the red coloring composition for color filters of the present invention, not only diketopyrrolopyrrole red pigments but also other red pigments, orange pigments and yellow pigments can be used in combination for the purpose of color adjustment and complementary color.

For example, as red pigments other than diketopyrrolopyrrole, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 246, 270, 279 and the like.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 181,182,185,187,188,193,194,198,199,213,214, and the like.
Examples of the orange pigment include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 and the like.

In addition, an inorganic pigment can be contained in order to ensure good coatability, sensitivity, developability and the like while balancing saturation and lightness. Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium Examples thereof include black, synthetic iron black, and carbon black. An inorganic pigment is used individually or in combination of 2 or more types. The inorganic pigment can be used in an amount of 0.1 to 10% by weight based on the total weight of the pigment (100% by weight).
Moreover, the red coloring composition for color filters of this invention can contain dye within the range which does not reduce heat resistance for color matching. The dye can be used in an amount of 0.1 to 10% by weight based on the total weight of the pigment (100% by weight).

The pigment is preferably miniaturized in order to achieve high brightness and high contrast of the color filter. As the finer processing method, a method of controlling the primary particle size and particle shape by mechanically pulverizing the pigment (referred to as grinding method), a solution dissolved in a good solvent into a poor solvent, and a desired primary particle size And a method of precipitating a pigment having a particle shape (referred to as a precipitation method) and a method of producing a pigment having a desired primary particle diameter or particle shape at the time of synthesis (referred to as a synthetic precipitation method). Depending on the synthesis method and chemical properties of the pigment to be used, an appropriate method can be selected for each pigment.
Each method will be described below, but any of the above methods may be used for the refining treatment of the pigment contained in the red coloring composition of the present invention.

  In the grinding method, the pigment is mechanically kneaded using a ball mill, sand mill or kneader together with a grinding agent such as water-soluble inorganic salt such as salt and a water-soluble organic solvent that does not dissolve it (hereinafter, this treatment is salted). This is a method of obtaining a pigment having a desired primary particle size and particle shape by washing and removing the inorganic salt and the organic solvent, followed by drying. However, since the pigment may crystallize by the salt milling treatment, a method of preventing crystal growth by adding a solid resin or a pigment dispersant that is at least partially dissolved in the organic solvent during the treatment is effective.

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. In general, 1 to 30 parts by weight, preferably 2 to 20 parts by weight of the inorganic salt is used per 1 part by weight of the pigment. The water-soluble organic solvent is added so that the pigment and the inorganic salt are uniformly solidified. Although depending on the blending ratio of the pigment and the inorganic salt, the water-soluble organic solvent is usually added in an amount of 0.1% by weight per 1 part by weight of the pigment. Used in an amount of 5 to 30 parts by weight.
More specifically, with respect to the above grinding method, 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 poured into water. Stir with a speed mixer to make a slurry. Next, this slurry is filtered, washed with water, and dried to obtain a pigment having a desired primary particle size and particle shape.

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 and particle shape. The type and amount of the solvent, the precipitation temperature, and the precipitation rate. The primary particle size and particle shape can be controlled by the above. In general, pigments are difficult to dissolve in solvents, so the solvents that can be used are limited, but examples include strongly acidic solvents such as concentrated sulfuric acid, polyphosphoric acid, chlorosulfonic acid, or basic solvents such as liquid ammonia, dimethylformamide solution of sodium methylate, etc. It has been known.
A typical example of this method 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 bad. Conversely, if the amount is too large, the treatment efficiency of the pigment is lowered. It is preferable. 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 and the work is dangerous. It will freeze at temperatures below this. The injection time is preferably 0.1 to 30 minutes with respect to 100 g of the pigment. As the time increases, the primary particle size tends to increase.

In addition, 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, it is possible to carry out the finer processing while taking into account the sized particle size of the pigment. It is more preferable because fluidity as a dispersion can be secured. At the time of salt milling or acid pasting, a dispersion aid such as a dye derivative, a resin-type pigment dispersant, or a surfactant can be used in combination in order to prevent aggregation of the pigment due to miniaturization. Further, by carrying out in the form of coexisting two or more kinds of pigments, even a pigment that is difficult to disperse by itself can be finished as a stable dispersion.
There is a leuco method as a special precipitation method. When a vat dye, such as a flavantron, perinone, perylene, or indanthrone, is reduced with alkaline hydrosulfite, the quinone group becomes a hydroquinone sodium salt (leuco compound) and becomes water-soluble. A pigment having a small primary particle size insoluble in water can be precipitated by adding an appropriate oxidizing agent to the aqueous solution for oxidation.

The synthetic precipitation method is a method in which a pigment having a desired primary particle size and particle shape is precipitated simultaneously with the synthesis of the pigment. However, when the produced fine pigment is taken out of 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 synthesized in water.
Furthermore, as a means for controlling the primary particle size and particle shape of the pigment, the primary particle size of the pigment is reduced 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 to disperse at the same time.

[Dye derivative]
The red coloring composition for a color filter of the present invention contains a diketopyrrolopyrrole dye derivative represented by the following general formula (1) and a thiazine indigo dye derivative represented by the following general formula (2). Since the diketopyrrolopyrrole pigment derivative has the same chemical structure as the diketopyrrolopyrrole red pigment, it has a strong adsorptive power on the surface of the diketopyrrolopyrrole red pigment, and it can cause crystal precipitation due to dispersion stabilization and high-temperature treatment. Has a suppressive effect. The thiazine indigo dye derivative has a structure similar to that of the diketopyrrolopyrrole pigment, and further has a functional group capable of hydrogen bonding (═O, ═NH). Therefore, the same effect on the diketopyrrolopyrrole red pigment as the diketopyrrolopyrrole pigment derivative is exhibited. Furthermore, since the hue is yellower than that of the diketopyrrolopyrrole pigment derivative, the effect on the decrease in transparency of the diketopyrrolopyrrole red pigment due to the increase in the blending amount is greater than that of the diketopyrrolopyrrole pigment derivative. Therefore, it is effective for maintaining high brightness.

式（１）において、Ｒ₁〜Ｒ₁₀は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、シアノ基、スルホニル基、カルボキシル基、ジアルキルアミノ基、ハロゲノアルキル基、アルコキシカルボニル基、アルキルメルカプト基、カルバモイル基、またはスルファモイル基を表し、Ｒ₁〜Ｒ₁₀の少なくとも１つはＥの結合手である。
式（２）において、Ｒ₁₁及びＲ₁₂は、それぞれ独立に、−（Ｅ）_ｑ−基以外の置換基を有していてもよい、芳香族または脂肪族炭素環または複素環を形成するために必要な基を表す。Ｒ₁₁を含む環及びＲ₁₂を含む環が有しうる置換基には、ハロゲン、ニトロ、シアノ、トリフルオロメチル、カルボンアミド、アルキル、アルコキシ、アミノ、アルキルアミノ、チオアルキル、フェノキシ、フェニルアミノ、フェニルチオ、アシル、アシルオキシ、アシルアミンアリール基が含まれる。Ｒ₁₁を含む環及びＲ₁₂を含む環は、−（Ｅ）_ｑ−基以外の置換基を有していてもよい芳香族炭素環であることが好ましく、−（Ｅ）_ｑ−基以外の置換基を有していてもよいベンゼン環であることが好ましい。
式（１）及び式（２）において、Ｅは、独立に、下記一般式（３）または下記一般式（４）で表される塩基性の置換基である。ｐは、１〜４、好ましくは１または２の整数を表し、ｑは、１〜６、好ましくは１〜４、さらに好ましくは１または２の整数を表す。

In Formula (1), R _{1 to} R ₁₀ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group, a sulfonyl group, a carboxyl group, a dialkylamino group, a halogenoalkyl group, an alkoxycarbonyl group, Represents an alkylmercapto group, a carbamoyl group, or a sulfamoyl group, and at least one of R _{1 to} R ₁₀ is a bond of E;
In formula (2), R ₁₁ and R ₁₂ each independently form an aromatic or aliphatic carbocycle or heterocycle which may have a substituent other than the — (E) _q — group. Represents a group necessary for. The substituents that the ring containing R ₁₁ and the ring containing R ₁₂ may have include halogen, nitro, cyano, trifluoromethyl, carbonamido, alkyl, alkoxy, amino, alkylamino, thioalkyl, phenoxy, phenylamino, phenylthio , Acyl, acyloxy, and acylamine aryl groups. Ring containing a ring and R ₁₂ contains a R ₁₁ is, _- (E) q - preferably have a substituent group other than group is also an aromatic carbocyclic, _- (E) q - other than group It is preferably a benzene ring which may have a substituent.
In the formulas (1) and (2), E is independently a basic substituent represented by the following general formula (3) or the following general formula (4). p represents an integer of 1 to 4, preferably 1 or 2, and q represents an integer of 1 to 6, preferably 1 to 4, and more preferably 1 or 2.

式（３）において、Ｒ₁₃及びＲ₁₄は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０、好ましくは１〜２５、さらに好ましくは１〜２０のアルキル基または置換基を有していてもよい炭素数２〜３０、好ましくは２〜２５、さらに好ましくは２〜２０のアルケニル基を表し、Ｒ₁₃及びＲ₁₄は窒素、酸素または硫黄原子を含む置換されてもよい複素環を形成していてもよい。Ｒ₁₃及びＲ₁₄が有しうる置換基には、上記Ｒ₁₁を含む環及びＲ₁₂を含む環が有しうる置換基が含まれる。Ｘは、−Ｓ−、−Ｏ−、−ＳＯ₂−、−ＣＯ−、−ＳＯ₂ＮＲ−、−ＮＲＳＯ_２−、−ＣＯＮＲ−、−ＣＨ₂ＮＲＣＯＣＨ₂ＮＲ−または−（ＣＨ₂）_ｍＮＨ−を表す。ｍは、１〜１０の整数を表す。各Ｒは、独立に、水素原子、置換基を有していてもよい炭素数１〜２０、好ましくは１〜１０、さらに好ましくは１〜６のアルキル基、置換基を有していてもよい炭素数２〜２０、好ましくは２〜１０、さらに好ましくは２〜６のアルケニル基または置換基を有していてもよい炭素数６〜２０、好ましくは６〜１０、さらに好ましくは６のアリール基を表す。Ｒが有しうる置換基には、上記Ｒ₁₁を含む環及びＲ₁₂を含む環が有しうる置換基が含まれる。ａは、０（Ｘの不存在）または１（Ｘの存在）を表す。Ｙは、置換基を有していてもよい炭素数１〜２０、好ましくは１〜１０、さらに好ましくは１〜６のアルキレン基、置換基を有していてもよい炭素数２〜２０、好ましくは２〜１０、さらに好ましくは2〜６のアルケニレン基、置換基を有していてもよい炭素数６〜２０、好ましくは６〜１０、さらに好ましくは６のアリーレン基または窒素、酸素または硫黄原子を含む置換されていてもよい複素環を表し、これらの基は、互いに直接結合していてもよいし、あるいは二つ以上組合せてもよく、−ＮＲ−、−Ｏ−、−ＳＯ₂−、−ＣＯ−または−ＣＯＮＨ−から選ばれる２価の連結基で互いに結合していてもよい。ここで、Ｒは上記定義の通りである。ｂは、０（Ｙの不存在）または１（Ｙの存在）を表す。

In the formula (3), R ₁₃ and R ₁₄ are each independently an optionally substituted alkyl group or substituent having 1 to 30 carbon atoms, preferably 1 to 25, more preferably 1 to 20 carbon atoms. Represents an alkenyl group having 2 to 30 carbon atoms, preferably 2 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, and R ₁₃ and R ₁₄ may be substituted containing a nitrogen, oxygen or sulfur atom. A heterocycle may be formed. The substituent that R ₁₃ and R ₁₄ may have includes the substituent that the ring containing R ₁₁ and the ring containing R ₁₂ may have. X is, -S -, - O -, - SO 2 -, - CO -, - SO 2 NR -, - NRSO 2 -, - CONR -, - CH 2 NRCOCH 2 NR- , or - (CH _{2) m} NH -Represents. m represents an integer of 1 to 10. Each R may independently have a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 6 carbon atoms, and a substituent. An aryl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms which may have an alkenyl group or a substituent, and preferably 6 to 10 carbon atoms, more preferably 6 carbon atoms. Represents. The substituent which R may have includes the substituent which the ring containing R ₁₁ and the ring containing R ₁₂ may have. a represents 0 (absence of X) or 1 (existence of X). Y is an optionally substituted alkylene group having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 6 carbon atoms, and optionally having 2 to 20 carbon atoms, preferably Is an alkenylene group having 2 to 10, more preferably 2 to 6, an optionally substituted aryl group having 6 to 20, preferably 6 to 10, and more preferably 6 or a nitrogen, oxygen or sulfur atom. Represents an optionally substituted heterocyclic ring, and these groups may be directly bonded to each other, or two or more thereof may be combined, and —NR—, —O—, —SO ₂ —, They may be bonded to each other through a divalent linking group selected from —CO— and —CONH—. Here, R is as defined above. b represents 0 (the absence of Y) or 1 (the presence of Y).

In the formula (4), R _{15 to} R ₁₈ are each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 6 carbon atoms. , Optionally having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms optionally having 6 to 20 carbon atoms, preferably 6 carbon atoms. Represents an aryl group of -10, more preferably 6. R ₁₉ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, or an optionally substituted carbon atom. Represents an alkenyl group of -20, preferably 2-10, more preferably 2-6. Z _{is, -CH 2 NR'COCH 2 NR '-} , - CH 2 NR'COCH 2 NR'-G -, - NR' -, - NR'-G-CO -, - NR'-G-CONR'- _{, -NR'-G-SO 2 -} , - NR'-G-SO 2 NR '-, - O-G-CO -, - O-G-CONR' -, - SO 2 -, - O-G- SO ₂ — or —O—G—SO ₂ NR′— is represented. G is an optionally substituted alkylene group having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 6 carbon atoms, and optionally having 2 to 20 carbon atoms, preferably Represents an arylene group having 2 to 10, more preferably 2 to 6 carbon atoms, or an optionally substituted arylene group having 6 to 20, preferably 6 to 10, more preferably 6. R ′ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 6 carbon atoms, and optionally having 2 substituents. -20, preferably 2 to 10, more preferably 2 to 6 alkenyl group or an optionally substituted aryl group having 6 to 20, preferably 6 to 10, more preferably 6 carbon atoms. The substituent which R ′ and G may have includes the substituent which the ring containing R ₁₁ and the ring containing R ₁₂ may have. c represents 0 (the absence of Z) or 1 (the presence of Z).

  In the red coloring composition for a color filter of the present invention, the contents of the diketopyrrolopyrrole pigment derivative represented by the general formula (1) and the thiazineindigo pigment derivative represented by the general formula (2) are the total Thus, it is preferably 15 to 40% by weight, more preferably 20 to 35% by weight of the pigment. When this content is less than 15% by weight, the pigment derivative is insufficient and the pigment dispersion becomes insufficient, which may increase the viscosity and lower the contrast. On the other hand, when it exceeds 40% by weight, the effect of suppressing crystal precipitation due to the high-temperature treatment of the diketopyrrolopyrrole red pigment is increased, but there is a possibility that the viscosity increase and lightness due to the excess dye derivative may decrease.

  In the present invention, the content of the diketopyrrolopyrrole dye derivative represented by the general formula (1) is preferably 2% by weight to 10% by weight, and more preferably 5% by weight to 8% by weight of the pigment. It is preferable that it is weight%. When this content is less than 2% by weight, the specific dispersion effect of the dye derivative having the same chemical structure as that of the diketopyrrolopyrrole red pigment and the effect of suppressing the crystallization are not sufficiently exhibited. On the other hand, when it exceeds 10% by weight, the transparency of the diketopyrrolopyrrole red pigment is affected, and the lightness is lowered.

  Specific examples of the diketopyrrolopyrrole dye derivative represented by the general formula (1) used in the red coloring composition for a color filter of the present invention include the following dye derivatives 5 to 18, Specific examples of the thiazineindigo dye derivative represented by the general formula (2) include the following dye derivatives 19 to 32, but the present invention is not limited thereto.

(Pigment carrier)
The pigment carrier contained in the red coloring composition for a color filter of the present invention disperses the pigment, and is composed of a resin, a precursor thereof, or a mixture thereof. The resin is a transparent resin having a transmittance of 80% or more, preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The resin includes a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin, and a precursor of the resin is a monomer or oligomer that is cured by irradiation with an active energy ray to form a resin (active energy ray curing). Monomer) and these may be used alone or in combination of two or more.
The pigment carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight, with respect to 100 parts by weight of the total pigment in the coloring composition. When a mixture of a resin and its precursor is used as a pigment carrier, the resin is 20 to 400 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the total pigment in the coloring composition. Can be used. The resin precursor can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the total pigment in the coloring composition.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.
Active energy ray-curable resins include (meth) acrylic having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting a compound or cinnamic acid is used. In addition, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  Active energy ray curable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxy. Ethyl (meth) acrylate, diethylene 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, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, ne Opentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, Various acrylic esters and methacrylic esters such as urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) Examples include acrylamide, N-vinylformamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the red coloring composition for a color filter of the present invention.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone compounds such as hydroxycyclohexyl phenyl ketone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl Benzoin photopolymerization initiators such as dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-ben Benzophenone photopolymerization initiators such as yl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, Thioxanthone photopolymerization initiators such as isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-Piperonyl-4,6-bis (trichloromethyl) -s-triazi 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, 2,4-trichloromethyl (4'-methoxystyryl)- Triazine-based photopolymerization initiators such as 6-triazine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1- Oxime ester photopolymerization initiators such as phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) fur Phosphine photopolymerization initiators such as nylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, quinone photopolymerization initiators such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone, borate light A polymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, a titanocene photopolymerization initiator, or the like is used. These photopolymerization initiators can be used alone or in combination. A photoinitiator can be used in the amount of 5-200 weight part with respect to a total of 100 weight part of the pigment in a coloring composition, Preferably it is 10-150 weight part.

  The photopolymerization initiators may be used alone or in combination of two or more. As sensitizers, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, Isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4 ′ An amine compound such as -bis (diethylamino) benzophenone or 4,4'-bis (ethylmethylamino) benzophenone can also be used in combination. These sensitizers can be used alone or in combination. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the colored composition.

  Furthermore, a polyfunctional thiol that functions as a chain transfer agent can be contained. The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto--s- triazine. These polyfunctional thiols can be used alone or in combination. The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the total pigment in the coloring composition.

[Other ingredients]
In the red coloring composition for a color filter of the present invention, it is preferable to use a solvent in order to sufficiently disperse the pigment in the pigment carrier and to apply it on the glass substrate so that the dry film thickness is 0.2 to 5 μm. it can. Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol , 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o- Xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene Glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol mono Hexyl ether, ethylene glycol monomethyl ether Ter, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone , Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dip Pyrene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether , Propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, Isobutyl, propyl acetate, dibasic esters, and the like, used alone or in combination. The solvent can be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight, based on 100 parts by weight of the total pigment in the coloring composition.

In addition, in the red coloring composition for a color filter of the present invention, a dispersion aid such as a resin-type pigment dispersant or a surfactant can be used in addition to the dye derivative for the purpose of stabilizing the dispersion of the pigment. .
The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and acts to stabilize the dispersion of the pigment on the pigment carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Oil-based dispersants such as salts; water-soluble such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based or the like is used. These can be used alone or in admixture of two or more.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monododecyl sulfate. Anionic properties such as ethanolamine, triethanolamine dodecyl sulfate, ammonium dodecyl sulfate, monoethanolamine stearate, sodium stearate, sodium dodecyl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Surfactant: Polyoxyethylene oleyl ether, polyoxyethylene dodecyl ether, polyoxyethylene nonylphenyl ether Nonionic surfactants such as tellurium, polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts Agents: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more.

  In addition, the red coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time, and in order to improve the adhesion to a transparent substrate, a silane cup An adhesion improving agent such as a ring agent can also be contained. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4- Epoxy cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltri Examples thereof include aminosilanes such as methoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  Moreover, it is preferable to add a leveling agent to the red coloring composition for color filters of this invention in order to improve the leveling property of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in 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 0.003 to 0.5% by weight based on the total weight (100% by 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 the leveling agent, 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.

The red coloring composition for a color filter of the present invention is a mixture of a pigment, a dye derivative, a dispersion aid, a resin, a solvent, etc., a three roll mill, a two roll mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, A pigment composition can be prepared by dispersing with an attritor or the like, and an active energy ray-curable monomer, an active energy ray polymerization initiator, or the like can be added.
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

Next, the color filter which comprises the red filter segment formed from the red coloring composition for color filters of this invention is demonstrated.
The color filter of the present invention comprises a red filter segment formed from the red coloring composition for a color filter of the present invention on a transparent substrate. The color filter of the present invention usually further comprises a green filter segment and a blue filter segment which are formed using a known coloring composition.
As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. Further, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after the liquid crystal panel is formed.

  Each color filter segment can be formed by, for example, a printing method, a photolithography method, or the like. The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as a printing ink. Therefore, the color filter manufacturing method is low in 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.

  The formation of each color filter segment by photolithography is performed by the following method. That is, the color composition for color filter prepared as a color composition for solvent development type or alkali development type color filter is applied on a transparent substrate such as glass by a coating method such as spray coating, spin coating, slit coating, roll coating or the like. It is applied so that the dry film thickness is 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used. If necessary, the dried film is subjected to active energy ray exposure through a mask having a predetermined pattern provided in contact or non-contact with the film. Thereafter, the color filter can be manufactured by immersing in a solvent or an alkali developer, or spraying the developer by spraying or the like to remove an uncured portion to form a desired pattern. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

  In developing the colored composition, 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. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. In order to increase the exposure sensitivity to active energy rays, a film that prevents polymerization inhibition by oxygen by applying and drying a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin after coating and drying the colored composition. After forming, active energy ray exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the above method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there.
The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet or transfer cylinder, and this filter segment is transferred to a desired transparent substrate.

  If a black matrix is formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, an inorganic film such as chromium, a chromium / chromium oxide multilayer film, titanium nitride, or a resin film in which a light shielding agent is dispersed may be used. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.
The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding. This liquid crystal display panel includes Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), and Optical Convencence Bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the examples, “parts” represents “parts by weight”.
a) Various measurement methods
[Viscosity measurement]
About the red coloring composition, the E type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) was used on the next day after the preparation, and the measurement was performed at 25 ° C under the condition of a rotation speed of 20 rpm.
[Chromaticity and contrast]
The red coloring composition was applied to a glass substrate by spin coating so that the chromaticity x after curing was 0.65 (C light source), dried at 70 ° C. for 20 minutes, and then using an ultrahigh pressure mercury lamp. UV light was exposed. Thereafter, this substrate was heat-treated at 230 ° C. for 1 hour to obtain a red colored film. The red colored film was measured for chromaticity (Y, x, y) with a C light source using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Further, polarizing plates were overlapped on both sides of the substrate on which the red colored film was formed, and the ratio of luminance (Lp) when the polarizing plates were parallel and luminance (Lc) when they were orthogonal, Lp / Lc was calculated as contrast. The luminance was measured using a color luminance meter (“BM-5A” manufactured by Topcon Corporation) under the condition of a 2 ° visual field. Contrast was measured for red colored films before and after the heat resistance test described below.

[Evaluation of crystal precipitation (heat resistance)]
In the color filter manufacturing step, ITO sputtering is performed after each color filter segment is formed. Usually, in this sputtering process, annealing is performed at a high temperature of 200 ° C. or higher. Therefore, as a condition for evaluating crystal precipitation, the red colored film obtained above was further heat-treated at 250 ° C. for 1 hour. And it observed with the optical microscope and evaluated in the following four steps.
A: No crystal precipitation was observed, and the surface condition was good.
○: No crystal precipitation was observed, but the surface was slightly rough.
Δ: Crystal precipitation is slightly observed, but is within the usable range.
X: Many crystals are precipitated and cannot be used.

b) Dye Derivatives The dye derivatives used in Examples and Comparative Examples are shown in Table 1. These pigment derivatives can be produced by the methods described in, for example, JP-A-3-26767, JP-B-1-34268, JP-B-5-72943, JP-A-2007-314785, and the like.

c) Preparation of red-treated pigment 100 parts of diketopyrrolopyrrole red pigment (CI Pigment Red 254, “Irgafore Red B-CF” manufactured by Ciba Japan), 1000 parts of ground salt, and 120 parts of diethylene glycol Was placed in a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C for 20 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. Dried to obtain 97 parts of red treated pigment.

d) Preparation of acrylic resin solution 370 parts of cyclohexanone was placed in a reaction vessel and heated to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, n- A mixture of 55.0 parts of butyl methacrylate, 15.0 parts of 2-hydroxyethyl methacrylate, and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained. The weight average molecular weight of the acrylic resin was about 40,000. After cooling to room temperature, about 2 g of the resin solution is sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content is measured. Based on the measurement result, the previously synthesized resin solution has a nonvolatile content of 20% by weight. An acrylic resin solution was prepared by adding cyclohexanone.

e) Preparation of Red Pigment Dispersion Mixtures having the composition shown in Table 2 were uniformly stirred and mixed, and zirconia beads having a diameter of 0.5 mm were used, and 3 by Eiger Mill (“Mini Model M-250 MKII” manufactured by Eiger Japan). After time dispersion, various pigment dispersions were obtained by filtration through a 5 μm filter. Table 2 also shows the weight% of the dye derivative relative to the pigment in each pigment dispersion.

f) Preparation of red colored composition and production of red colored film [Example 1]
Using a pigment dispersion (RP-1), a mixture having the following blending ratio was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a red coloring composition. The viscosity of the coloring composition was measured. Moreover, the obtained red coloring composition was apply | coated to the glass substrate, the red coloring film was produced, and chromaticity, contrast, and crystal precipitation (heat resistance) were evaluated. The results are shown in Table 3.
-Pigment dispersion (RP-1): 44.8 parts-Previously prepared acrylic resin solution: 23.2 parts-Trimethylolpropane triacrylate: 1.7 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
-2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one ("Irgacure 907" manufactured by Ciba Japan): 0.5 part-Propylene glycol monomethyl ether acetate: 29. 8 copies

[Example 2]
Red colored compositions corresponding to Examples 2 to 8, respectively, in the same manner as in Example 1, except that the pigment dispersion (RP-1) was replaced with pigment dispersions (RP-2) to (RP-8). And a red colored film was obtained. Table 3 shows the viscosity of the obtained red coloring composition, the chromaticity of the red coloring film, the contrast, and the results of the heat resistance test.
[Comparative Examples 1 to 7]
Red colored compositions corresponding to Comparative Examples 1 to 7, respectively, in the same manner as in Example 1 except that the pigment dispersion (RP-1) was replaced with pigment dispersions (RP-9) to (RP-15). And a red colored film was obtained. Table 3 shows the viscosity of the obtained red coloring composition and the chromaticity, contrast, and heat resistance test of the obtained red coloring film.

  As shown in Table 3, in the red colored composition and the red colored film obtained in Examples 1 to 8 containing a diketopyrrolopyrrole dye derivative or a thiazine indigo dye derivative, viscosity, lightness, and heat resistance It can be seen that the balance is good in contrast, and the contrast is excellent. On the other hand, it can be seen that the red colored composition and the red colored film obtained in Comparative Examples 1 to 5 containing only either the diketopyrrolopyrrole pigment derivative or the thiazineindigo pigment derivative have poor property balance. . In Comparative Example 4, although the heat resistance is good, the brightness is poor because the content of the diketopyrrolopyrrole pigment derivative is large. Moreover, the red colored composition and the red colored film obtained in Comparative Examples 6 and 7 containing a dye derivative other than a diketopyrrolopyrrole dye derivative and a thiazineindigo dye derivative have poor heat resistance.

Claims (5)

A pigment carrier comprising a resin, a precursor thereof or a mixture thereof, a diketopyrrolopyrrole red pigment, a diketopyrrolopyrrole dye derivative represented by the following general formula (1), and a thia represented by the following general formula (2) A red coloring composition for a color filter, comprising a ginindigo dye derivative.

In Formula (1), R _{1 to} R ₁₀ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group, a sulfonyl group, a carboxyl group, a dialkylamino group, a halogenoalkyl group, an alkoxycarbonyl group, Represents an alkylmercapto group, a carbamoyl group, or a sulfamoyl group, and at least one of R _{1 to} R ₁₀ is a bond of E; p represents an integer of 1 to 4. In formula (2), R ₁₁ and R ₁₂ each independently form an aromatic or aliphatic carbocycle or heterocycle which may have a substituent other _than- (E) _q group. Represents the necessary group. In formula (1) and formula (2), E independently represents the following general formula (3) or the following general formula (4). q represents the integer of 1-6.

In Formula (3), R ₁₃ and R ₁₄ are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent or an alkyl group having 2 to 30 carbon atoms which may have a substituent. Represents an alkenyl group, and R ₁₃ and R ₁₄ may form an optionally substituted heterocyclic ring containing a nitrogen, oxygen or sulfur atom. X is, -S -, - O -, - SO 2 -, - CO -, - SO 2 NR -, - NRSO 2 -, - CONR -, - CH 2 NRCOCH 2 NR- , or - (CH _{2) m} NH -(Wherein m represents an integer of 1 to 10. R independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. An alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent). a represents 0 or 1; Y is an optionally substituted alkylene group having 1 to 20 carbon atoms, an optionally substituted alkenylene group having 2 to 20 carbon atoms, and an optionally substituted carbon number. 6-20 arylene group or a nitrogen, oxygen or (these groups representing a heterocyclic ring which may be substituted containing a sulfur atom may be combined two or more, -NR -, - O -, - SO 2 And may be bonded to each other through a divalent linking group selected from-, -CO- and -CONH-, wherein R is as defined above. b represents 0 or 1. In the formula (4), R _{15 to} R ₁₈ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon number 2. Represents an aryl group having 6 to 20 carbon atoms which may have -20 alkenyl groups or substituents; R ₁₉ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted alkenyl group having 2 to 20 carbon atoms. Z _{is, -CH 2 NR'COCH 2 NR '-} , - CH 2 NR'COCH 2 NR'-G -, - NR' -, - NR'-G-CO -, - NR'-G-CONR'- _{, -NR'-G-SO 2 -} , - NR'-G-SO 2 NR '-, - O-G-CO -, - O-G-CONR' -, - SO 2 -, - O-G- Represents SO ₂ — or —O—G—SO ₂ NR′— (G represents an optionally substituted alkylene group having 1 to 20 carbon atoms and optionally substituted carbon atoms. Represents a 2-20 alkenylene group or an optionally substituted arylene group having 6 to 20 carbon atoms, and R ′ represents a hydrogen atom or an optionally substituted alkyl having 1 to 20 carbon atoms. Group, an alkenyl group having 2 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 20 carbon atoms which may have a substituent. c represents 0 or 1;   The red coloring composition for a color filter according to claim 1, further comprising an active energy ray-curable monomer and a photopolymerization initiator.   3. The red coloring composition for a color filter according to claim 1, wherein the total content of the diketopyrrolopyrrole pigment derivative and the thiazineindigo pigment derivative is 15 wt% to 40 wt% of the weight of the pigment. object.   The red coloring composition for a color filter according to claim 3, wherein the content of the diketopyrrolopyrrole pigment derivative is 2% by weight to 10% by weight of the pigment.   A color filter comprising a red filter segment formed from the red coloring composition for a color filter according to claim 1.