JP2013101287A - Coloring composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a blue coloring composition for a color filter, which is excellent in heat resistance and NMP resistance and satisfies solubility to a solvent, and provide a color filter including the blue coloring composition, which is excellent in color characteristics.SOLUTION: A coloring composition for a color filter includes a colorant [A], a resin [B], and an isocyanurate compound [C]. A color filter includes a filter segment formed of the coloring composition for a color filter on a substrate.

Description

  The present invention includes a color liquid crystal display device, a color filter coloring composition used for manufacturing a color filter used for a color image pickup tube element, and the like, and a filter segment and / or a black matrix formed using the same. The present invention relates to a color filter.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The display device performs display, and color display is possible by providing a color filter between two polarizing plates.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine colored (striped) colored pixel layers having different hues are arranged in parallel or intersecting, or a fine colored pixel layer is vertically and horizontally constant. It consists of things arranged in an array. The colored pixel layer is as fine as several microns to several hundreds of microns, and is arranged regularly in a predetermined arrangement for each hue.

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

Quality items required for the color filter include contrast ratio, brightness, heat resistance, solvent resistance, and the like.
When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

  If a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend.

  In this way, with the demand for higher brightness and higher contrast of the color filter, the pigment is made finer, the heat resistance is reduced accordingly, and the lightness in the color filter forming process is reduced, and It is required to suppress the color difference ΔEab * (the brightness does not decrease even when exposed to high temperatures in the post-baking, transparent electrode, and alignment film forming process, and the color difference ΔEab * is small).

  In general, a liquid crystal display device is manufactured by sandwiching a liquid crystal between a separately produced color filter substrate and a TFT (Thin-Film-Transistor) substrate. At this time, the color filter substrate aligns the liquid crystal by applying an alignment film such as polyimide on the colored layer. For this reason, the colored layer is required to have resistance to a highly polar solvent such as NMP (N-methyl-pyrrolidone) contained in the polyimide resin.

However, the color filter formed from the conventional coloring composition has a drawback that the chromaticity is largely changed by high temperature or NMP.
In order to improve such a problem, Patent Document 1 proposes a color filter coloring composition containing hexaarylbiimidazole for the purpose of increasing crosslinking efficiency by increasing sensitivity and increasing NMP resistance. Yes. However, in this method, the effect on NMP resistance is not sufficient, and there are problems such as a large change in chromaticity after immersion in NMP.

  In addition, Patent Document 2 has been known to improve curability and heat resistance by using tris- (2,3-epoxypropyl) -isocyanurate, which is an isocyanurate compound. It has been a problem that crystal compatibility is very poor and crystals are precipitated, and it has been proposed to improve by mixing monofunctional and bifunctional epoxy resins.

JP-A-6-148417 JP 2004-217780 A

  An object of the present invention is to provide a coloring composition for a color filter that satisfies NMP resistance (change in chromaticity) and heat resistance, and that does not generate foreign matter on a coating film due to poor solubility due to a solvent, and the coloring composition for a color filter. It is providing the high quality color filter formed using.

  As a result of intensive studies to achieve the above object, the present inventors have focused on the high-density cross-linking performance and rigid skeleton possessed by the isocyanurate compound, and as a result, have NMP resistance (color change). It has been found that the satisfaction and heat resistance are satisfied, and the present invention has been achieved based on this finding.

[一般式（１）中、Ｒ₁はそれぞれ独立に、一般式（２）、または一般式（３）で表される基であるが、少なくとも１つは、一般式（３）で表される基である]

[一般式（３）中、Ｒ₂は置換されてもよい炭素数１〜２０のアルキル基である。Ｒ₃は、水素原子、または一般式（４）で表される基である]

[一般式（４）中、Ｒ₄は置換されてもよい炭素数１〜２０のアルキル基である]
That is, this invention relates to the coloring composition for color filters characterized by containing the colorant [A], resin [B], and compound [C] represented by General formula (1) at least.

[In General Formula (1), each R ₁ is independently a group represented by General Formula (2) or General Formula (3), but at least one is represented by General Formula (3) Is the group]

[In General Formula (3), R ₂ is an optionally substituted alkyl group having 1 to 20 carbon atoms. R ₃ is a hydrogen atom or a group represented by the general formula (4)]

[In General Formula (4), R ₄ is an optionally substituted alkyl group having 1 to 20 carbon atoms]

In the present invention, the compound [C] represented by the general formula (1) is a group in which two of R ₁ are represented by the general formula (2), and the other is represented by the general formula (3). And a coloring composition for a color filter, which comprises a compound which is a group to be colored.

In the present invention, the compound [C] represented by the general formula (1) is a group in which one of R ₁ is represented by the general formula (2), and the other two are represented by the general formula (3). And a coloring composition for a color filter, comprising a compound as a group.

The present invention further relates to the above colored composition for a color filter, wherein the R _{1 in the} general formula (1) contains a compound in which all R ₁ are groups represented by the general formula (3).

  The present invention also relates to the above color composition for color filter, which further contains a polyfunctional monomer [D] and / or a photopolymerization initiator [E].

  The present invention also relates to the above color filter coloring composition, wherein the colorant [A] contains a dye or a salt-forming compound thereof [A1].

  Moreover, this invention relates to the color filter formed by shape | molding the said coloring composition for color filters.

  The colored composition for a color filter of the present invention makes it possible to form a colored pixel layer satisfying heat resistance and NMP resistance (chromaticity change) and brightness, which have been difficult until now.

First, various components of the coloring composition for a color filter of the present invention will be described.
In the present application, when expressed as “(meth) acrylate”, “(meth) acrylic acid”, or “(meth) acrylamide”, unless otherwise specified, “acrylate and / or methacrylate”, It shall represent “acrylic acid and / or methacrylic acid” or “acrylamide and / or methacrylamide”.
Further, “CI” mentioned below means a color index (CI).

[Colorant (A)]
The coloring composition for a color filter of the present invention is characterized by containing one or more of a xanthene dye (A1) or an organic pigment (A2) as a colorant.

<Xanthene dye (A1)>
The xanthene colorant (A1) that can be preferably used in the present invention has a red or purple color, preferably has a dye form, and is either an oil-soluble dye, an acid dye, a direct dye, or a basic dye. It is preferable that it has the form. Moreover, it may be in the form of a lake pigment obtained by lacquering these dyes.
Among these, it is preferable to use a xanthene oil-soluble dye and a xanthene acid dye because of excellent hue.

A red or purple color means C.I. I. Solvent Red, C.I. Oil soluble dyes such as I. solvent violet, C.I. I. Basic Red, C.I. Basic dyes such as I. basic violet, C.I. I. Acid Red, C.I. Acid dyes such as I. acid violet, C.I. I. Direct Red, C.I. I. Direct dyes such as direct violet, and the like.
Here, the direct dye has a sulfonic acid group (—SO ₃ H, —SO ₃ Na) in the structure, and in the present invention, the direct dye is regarded as an acid dye.

  The xanthene dye (A) used in the present invention has a transmittance of 90% or more in the region of 650 nm in the transmission spectrum, a transmittance of 75% or more in the region of 600 nm, and a transmittance of 5% in the region of 500 to 550 nm. Hereinafter, those having a transmittance of 70% or more in the 400 nm region are preferable. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance is 10% or less in the region of 500 to 550 nm, and the transmittance is 75% in the region of 400 nm. That's it.

Among them, xanthene basic dyes and xanthene acid dyes have spectral characteristics with high transmittance at 400 to 450 nm, but have problems with light resistance and heat resistance and require high reliability. The characteristics may not be sufficient for use in an image display device using a color filter.
Therefore, in order to improve these drawbacks, the xanthene-based basic dye is preferably used after being salted using an organic acid or perchloric acid. As the organic acid, organic sulfonic acid or organic carboxylic acid is preferably used. Of these, naphthalenesulfonic acid such as tobias acid and perchloric acid are preferably used in terms of resistance.
In addition, xanthene-based acid dyes are used as salt-forming compounds by salt formation using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., and resin components having these functional groups. In view of resistance, it is preferable to use it as a sulfonamide compound after sulfonamidation.

  Among these, a salt component of a xanthene acid dye and / or a sulfonic acid amide compound of a xanthene acid dye is preferable because of excellent hue and resistance, and further, a counter component that functions as a counter ion. It is more preferable to use a compound prepared by using a quaternary ammonium salt compound and a sulfonic acid amide compound obtained by sulfonamidating a xanthene acid dye.

  Of the xanthene dyes (A), rhodamine dyes are preferred because they are excellent in color developability and resistance.

  Hereinafter, the form of the xanthene dye (A) used in the present invention will be specifically described in detail.

(Xanthene oil-soluble dye)
Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10 and the like.
Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.

(Xanthene basic dye)
Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like. Among these, C.I. I. Basic Red 1, C.I. I. Basic violet 10 is preferably used.

(Xanthene acid dyes)
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

(Salt forming compound of xanthene acid dye and / or sulfonic acid amide compound of xanthene acid dye)
In the present invention, the xanthene-based acidic dye is formed by chlorination using a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, etc., and a resin component having these functional groups, It is preferable to use a salt-forming compound of the above, or to sulfonamid to give a sulfonic acid amide compound because high heat resistance, light resistance, and solvent resistance can be imparted.

  Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetra Examples include aliphatic unsaturated primary amines such as decylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, cured tallow alkylamine, allylamine, aniline, and benzylamine. .

  Secondary amine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl. Amine, di-cured tallow alkylamine, distearylamine, etc.

  Examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine and the like.

  Among the xanthene dyes (A) used in the present invention, it is particularly preferable to use xanthene acid dyes by chlorination using quaternary ammonium salts or sulfonamidation of xanthene acid dyes. One form is explained in full detail below.

[Salt-forming compound comprising xanthene acid dye and quaternary ammonium salt compound]
The xanthene dye (A) used in the present invention is most preferably used as a salt-forming compound composed of the above-mentioned xanthene acid dye and a quaternary ammonium salt compound from the viewpoint of heat resistance, light resistance and solvent resistance. .

-Quaternary ammonium salt compound A quaternary ammonium salt compound has an amino group, and the cation part becomes a counter of a xanthene acid dye.

  A preferred form of the quaternary ammonium salt compound that is a counter component of the salt-forming compound is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Is. That is, it is necessary not to inhibit color development of the dye component and to cause no color change.

The molecular weight of the cation moiety serving as a counter for the quaternary ammonium salt compound is preferably in the range of 190 to 900. Here, the cation moiety corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) ⁺ moiety in the following general formula (4). When the molecular weight is smaller than 190, light resistance and heat resistance are lowered, and the solubility in a solvent may be further lowered. On the other hand, when the molecular weight is larger than 900, the ratio of the coloring component in the molecule is lowered, so that the color developability is lowered and the lightness is also lowered. More preferably, the molecular weight of the cation moiety is in the range of 240 to 850, and particularly preferably in the range of 350 to 800.
Here, the molecular weight was calculated based on the structural formula. The atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

  Moreover, the compound represented by following General formula (5) can be used as a quaternary ammonium salt compound.

[一般式（５）中、Ｒ₁〜Ｒ₄は、それぞれ独立に、炭素数１〜２０のアルキル基またはベンジル基を示し、Ｒ₁、Ｒ₂、Ｒ₃、又はＲ₄の少なくとも２つ以上が、Ｃの数が５〜２０個である。Ｙは無機または有機のアニオンを表す。] General formula (5)

[In General Formula (5), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ , or R ₄ However, the number of C is 5-20. Y represents an inorganic or organic anion. ]

The solubility with respect to a solvent becomes favorable because the number of C of the side chain of at least 2 of R < ₁ > -R < ₄ > shall be 5-20. When R _{1 to} R ₄ have 3 or more alkyl groups having a C number smaller than 5, the solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Further, if an alkyl group having a C number exceeding 20 is present in the side chain, the color forming property of the salt-forming compound may be impaired.

  The Y-component constituting the anion of the quaternary ammonium salt compound may be an inorganic or organic anion, but is preferably a halogen, usually chlorine.

Specific examples of such quaternary ammonium salt compounds include tetramethylammonium chloride (with a molecular weight of the cation moiety of 74), tetraethylammonium chloride (with a molecular weight of the cation moiety of 122), and monostearyltrimethylammonium chloride (with a molecular weight of the cation moiety). 312), distearyldimethylammonium chloride (cation part molecular weight 550), tristearyl monomethylammonium chloride (cation part molecular weight 788), cetyltrimethylammonium chloride (cation part molecular weight 284), trioctylmethylammonium chloride ( The molecular weight of the cation moiety is 368), dioctyldimethylammonium chloride (the molecular weight of the cation moiety is 270), monolauryltrimethyla Monium chloride (cation part molecular weight 228), dilauryldimethylammonium chloride (cation part molecular weight 382), trilaurylmethylammonium chloride (cation part molecular weight 536), triamylbenzylammonium chloride (cation part molecular weight 318), trihexylbenzylammonium chloride (cation part molecular weight 360), trioctylbenzylammonium chloride (cation part molecular weight 444), trilaurylbenzylammonium chloride (cation part molecular weight 612), benzyldimethylstearylammonium chloride (Molecular weight of the cation moiety is 388) and benzyldimethyloctyl ammonium chloride (molecular weight of the cation moiety is 248) , Or dialkyl (alkyl C ₁₄ -C ₁₈₎ dimethyl ammonium chloride (hydrogenated tallow) (molecular weight of the cationic moiety is from 438 to 550) is preferably used and the like.

As products, Cotamin 24P, Cotamin 86P Conch, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50, etc. manufactured by Kao Corporation, Lion Corporation's Arcade 210-80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75 or 2HP flakes and the like, among others QUARTAMIN D86P (distearyldimethylammonium chloride), or Arquad 2HT-75 (di (alkyl C ₁₄ -C ₁₈₎ dimethyl ammonium chloride) Etc. are preferable.

  The quaternary ammonium salt compound may be in the form of a resin having a cationic group, particularly an amino group or an ammonium group in the side chain, and capable of forming a quaternary ammonium salt structure by reacting and salting with a xanthene acid dye. .

-Manufacturing method of salt-forming compound The salt-forming compound of a xanthene acid dye and a quaternary ammonium salt compound can be manufactured by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969.
For example, after the xanthene acid dye is dissolved in water, the quaternary ammonium salt compound is added and the chlorination treatment may be performed while stirring. Here, the sulfonic acid group (—SO ₃ H), sodium sulfonate group (—SO ₃ Na) part in the xanthene acid dye and the ammonium group (NH ₄ ⁺ ) part of the quaternary ammonium salt compound are combined. A salt compound is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used for the chlorination.

Examples of the salt-forming compound include C.I. I. Acid Red 289 and C.I. I. By using a salt-forming compound of Acid Red 52 and a quaternary ammonium salt compound having a molecular weight of the counter cation moiety of 350 to 800, it has excellent solvent solubility and is more heat resistant when used in combination with a pigment described later. Excellent in light resistance, light resistance and solvent resistance. In addition, it is presumed that the salt formation compound that is favorable when used in combination with the pigment is adsorbed on the pigment while being dissolved and dispersed in the solvent. At this time, the primary particle diameter of the pigment is preferably 20 to 100 nm.
Although the coloring composition of this invention is mentioned later, the form of the blue coloring composition used together with a blue pigment and the red coloring composition used together with a red pigment is preferable.

[Sulfonic acid amide compound of xanthene acid dye]
A sulfonic acid amide compound of a xanthene acid dye that can be preferably used in the xanthene dye (A) of the present invention is obtained by chlorinating a xanthene acid dye having —SO ₃ H and —SO ₃ Na by a conventional method, SO ₃ H can be made —SO ₂ Cl, and this compound can be produced by reacting with an amine having an —NH ₂ group.
Specific examples of amine compounds that can be preferably used in sulfonamidation include 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, and 3-ethoxypropyl. It is preferable to use amine, cyclohexylamine or the like.
For example, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 289 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 289.
In addition, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 52 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 52 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 52.

<Organic pigment [A2]>
Further, specific examples of pigments that can be used in the present invention when forming color filter pixels as the colorant [A] are shown.
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254, more preferably C.I. I. Pigment Red 177, 209, 224, 242, or 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 or 58.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, or 180.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

[Miniaturization of pigment]
The pigment used in the present invention can be refined by a salt milling process or the like. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the pigment carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. In addition, the primary particle diameter of a pigment has the method of measuring the magnitude | size of a primary particle directly from the electron micrograph by TEM (transmission electron microscope) of a pigment, for example. Specifically, for example, the short axis diameter and the long axis diameter of the primary particle of each pigment are measured in nm units, and the average is the primary particle diameter of the pigment particle. There is a method of calculating the number average particle diameter by obtaining the volume of the particles, performing this operation for 100 pigment particles, and calculating based on the respective particle diameters and volumes.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

  When preparing a pigment dispersion, add pigment derivatives to prevent aggregation of the pigment, maintain a finely dispersed state of the pigment, and produce a color filter with high brightness and high contrast ratio and high color purity. Is preferred. The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the pigment. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by weight or less, and most preferably 35 parts by weight or less with respect to 100 parts by weight of the pigment.

  A pigment derivative is a compound in which a basic or acidic substituent is introduced into an organic dye. Organic dyes include light yellow aromatic polycyclic compounds that are not generally called dyes, such as naphthalene, anthraquinone, and acridone. Examples of the pigment derivative include JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-9-9. 176511 gazette etc. can be used, and these can be used individually or in mixture of 2 or more types.

  The coloring composition for a color filter of the present invention can be added with a resin-type dispersant that is excellent in pigment dispersibility and has a large effect of preventing reaggregation of the pigment after dispersion. The resin-type dispersant can be used in an amount of preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment.

  The resin-type dispersant has an acidic group or a basic group because it adsorbs to the surface of the pigment using an acidic group or a basic group as an anchor, and the rebound effect of the polymer acts effectively to express dispersion stability. A polymer is preferred. The acidic group is preferably a sulfone group from the viewpoint of excellent adsorption characteristics, and the basic group is preferably an amino group from the viewpoint of excellent adsorption characteristics. Also, the combined use of a pigment derivative having an acidic group and a resin type dispersant having a basic group, or a combined use of a pigment derivative having a basic group and a resin type dispersant having an acidic group has good compatibility with the resin. Therefore, it is preferable.

  As a resin type dispersant having an acidic group or a basic group, a comb polymer having a structure in which a branch polymer part is graft-bonded to a trunk polymer part having an acidic group or a basic group has an excellent steric repulsion effect of the branch polymer part. It is preferable because it is more soluble in organic solvents. Furthermore, a comb polymer having a molecular structure in which two or more branch polymers are grafted to one molecule of the trunk polymer is more preferable for the above reason.

  Commercially available resin-type dispersants include DisPerByk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171 manufactured by Big Chemie. 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-TerrA-U, 203, 204, or BYK-P104, P104S, 220S, or LACtimon, LACtimon-WS or Bykumen, etc. SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, manufactured by Nippon Lubrizol 2000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402 manufactured by Efka Chemicals , 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, and the like.

<Other colorants>
The coloring composition for a color filter of the present invention may be used in combination with a dye other than a xanthene dye as another colorant.

<Binder resin [B]>
The colored composition for a color filter of the present invention preferably further contains a binder resin [B]. By including the binder resin [B], the dispersion stability of the colored composition of the present invention becomes better, and when the colored pixel layer of the color filter is formed using the colored composition for a color filter, It is possible to obtain a colored pixel layer with a small amount of developability and good pattern shape.

The binder resin [B] 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.
Further, a thermoplastic resin is preferable, and when used in the form of an alkali developing type colored resist material, it is preferable to use an alkali-soluble resin copolymerized with an 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. This is more preferable because the photocuring density is increased, and as a result, resistance is improved.

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

Examples of the alkali-soluble resin obtained by copolymerizing 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 into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

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

  Examples of the ethylenically unsaturated 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 ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

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

  Examples of the ethylenically unsaturated monomer 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 ethylenically unsaturated 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.

  The weight average molecular weight (Mw) of the binder tree [B] fat is preferably in the range of 10,000 to 100,000, more preferably 10,000 to 80,000 in order to disperse the colorant [A] preferably. Range. 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 [B] is used as a photosensitive coloring composition for a color filter, a resin having an acid value of 20 to 300 mgKOH / g is used from the viewpoints of dispersibility, permeability, developability, and resistance of the pigment. Is preferred. 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 [B] is preferably used in an amount of 20 parts by weight or more with respect to 100 parts by weight of the colorant [A] because the film formability and various resistances are good, and the colorant concentration is high and good. Since color characteristics can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

<Isocyanurate Compound [C]>
The coloring composition for a color filter of the present invention contains an isocyanurate compound [C] represented by the general formula (1). By including the isocyanurate compound [C], the heat resistance and lightness are greatly improved by the heat-resistant structure of the isocyanurate compound [C] having a rigid nurate skeleton.

  The isocyanurate compound [C] is a compound represented by the general formula (1) and having 0 to 2 epoxy groups in one molecule, which is preferable from the viewpoint of curability and solubility in a solvent. Is preferably a mixture of a compound having three epoxy groups in one molecule and a compound having one or more epoxy groups in one other molecule. Among these, from the viewpoint of solvent resistance, it is more preferable that a compound having three epoxy groups in one molecule and a compound having two epoxy groups in one molecule are mixed. Above all, from the viewpoint of compatibility between solvent resistance and solubility in a solvent, a compound having three epoxy groups in one molecule, a compound having two epoxy groups in one molecule, It is more preferable that a compound having one epoxy group is mixed. Among them, when the total isocyanurate compound is 100 parts by weight, the internal ratio is 15 to 90 parts by weight of the compound having 3 epoxy groups in one molecule and 2 epoxy groups in one molecule. A mixture in which the mixing ratio of the compound is 5 to 80 parts by weight and the mixing ratio of the compound having one epoxy group in one molecule is 0 to 50 parts by weight is more preferable. Among them, the internal ratio is 30 to 80 parts by weight of the compound having three epoxy groups in one molecule, the mixing ratio of the compound having two epoxy groups in one molecule is 10 to 60 parts by weight, and one molecule. A mixture in which the mixing ratio of the compound having one epoxy group in the ratio of 0 to 40 parts by weight is more preferable.

  More preferable isocyanurate compound [C] is preferably a compound in which the group represented by the general formula (3) is carboxylic anhydride from the viewpoint of solubility in a solvent. Especially, it is more preferable that group represented by General formula (3) is a propionic anhydride from a viewpoint of coexistence with solvent resistance and solubility with a solvent.

  The content of the isocyanurate compound [C] is 1 to 250 parts by weight, preferably 5 to 150 parts by weight with respect to 100 parts by weight of the colorant [A] in the color filter coloring composition. When the isocyanurate compound [C] is included in an amount exceeding 250 parts by weight, the addition amount of a polyfunctional monomer, a photopolymerization initiator, etc. is limited, and sufficient developability cannot be secured, and dispersion stability may be a problem. is there. Conversely, when the isocyanurate compound [C] is contained in an amount of less than 1 part by weight, both the heat resistance and the NMP resistance (chromaticity change) may be insufficient because the cured density of the coating film is low.

  Moreover, in order to assist hardening of isocyanurate compound [C], the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited, and can react with thermosetting compounds. Any curing agent may be used as long as it is. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4 -Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of isocyanurate compound [C].

<Polyfunctional monomer [D]>
As the polyfunctional monomer [D], trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified To increase polyfunctional monomer [D1] having an acidic group, such as various acrylic acid esters and methacrylic acid esters such as trimethylolpropane tri (meth) acrylate, or a photopolymerizable monomer in which polymerization is partially induced by radicals Can do.

(Polyfunctional monomer having an acidic group [D1])
Examples of the polyfunctional monomer [D1] having an acidic group include an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polycarboxylic acid; Examples include esterified products with monohydroxyalkyl (meth) acrylates. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like monohydroxy oligoacrylates or monohydroxy oligomethacrylates And monoesterified products containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. be able to.

Moreover, the compound represented by following General formula (4) can also be used preferably.
General formula (4)
_{(H 2 C = C (R} 10) COO) m -X- (OCOCH (R 10) CH 2 S (R 11) COOH) n

[In General Formula (4), R ₁₀ is a hydrogen atom or a methyl group, R ₁₁ is a hydrocarbon group having 1 to 12 carbon atoms, X is an (m + n) -valent organic group having 3 to 60 carbon atoms, m is 2 to 2 The integer of 18 and n show the integer of 1-3. ]
Here, the compound represented by the following general formula (4) can be easily obtained, for example, by the following method.

(1) A method of adding a mercapto compound to an obtained compound after esterifying the compound giving an organic group represented by X with acrylic acid to acrylate, and (2) a compound giving an organic group represented by X Is modified with a polyisocyanate compound, and then the obtained compound is acrylated with an acrylate compound having a hydroxyl group, and then a mercapto compound is added to the obtained compound (3) to give an organic group represented by X A method in which a compound is esterified with acrylic acid to be acrylated, then modified with a polyisocyanate compound, and a mercapto compound is added to the obtained compound.

  Examples of compounds that give an organic group represented by X include pentaerythritol, pentaerythritol modified caprolactone, pentaerythritol modified polyisocyanate, dipentaerythritol, dipentaerythritol modified caprolactone, and dipentaerythritol polyisocyanate. Denatured products can be mentioned.

  Examples of mercapto compounds include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.

  The content of the polyfunctional monomer [D] is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant [A], and 10 to 300 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

<Photopolymerization initiator [E]>
Examples of the photopolymerization initiator [E] include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, etc. Acetophenone compounds, benzoin, benzoin methyl ether, benzoin ethyl ether Benzoin compounds such as benzoin isopropyl ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethyl Thioxanthone compounds such as thioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazi 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl- 4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (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) -6-triazine and other triazine compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O Benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, and other oxime ester compounds, bis (2,4,6 -Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetra Phenyl-1,2'-biimidazole, 2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl)- Imidazole compounds such as 4,4 ′, 5,5′-tetra (p-methylphenyl) biimidazole, 9,10-phenanthrenequinone, potassium Use may be made of quinone-based compounds such as nephroquinone and ethylanthraquinone, borate-based compounds, carbazole-based compounds, titanocene-based compounds and the like.
These photopolymerization initiators [E] can be used singly or as a mixture of two or more at any ratio as required.

  Among these, it is more preferable that the photopolymerization initiator [E] includes an acetophenone compound or an oxime ester compound. Since the acetophenone compound and the oxime ester compound are very sensitive, the content of the photopolymerization initiator [E] can be reduced. As a result, the brightness as a color filter can be improved, which is preferable.

  These photopolymerization initiators [E] are preferably 5 to 200 parts by weight with respect to 100 parts by weight of the colorant [A] in the color filter coloring composition, from the viewpoint of photocurability and developability. More preferably, it is 10 to 150 parts by weight.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by 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, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives and the like.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Among the sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator [F] contained in the colored composition, and is 5 to 5 from the viewpoint of photocurability and developability. More preferably, it is 50 parts by weight.

<Solvent>
The coloring composition for a color filter of the present invention is obtained by sufficiently dispersing the colorant [A] in a dye carrier such as a binder resin [B] or a polyfunctional monomer [E], and drying the film on a transparent substrate such as a glass substrate. It is used to make it easy to form a filter segment or a black matrix by coating so as to have a thickness of 0.2 to 10 μm.

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-butylal 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 Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Recall monobutyl ether, dipropylene glycol monopropyl ether, dipropylene 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 Tons, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  The solvent can be used in an amount of 100 to 10,000 parts by weight, preferably 500 to 5000 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

<Multifunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups.
When the polyfunctional thiol is used together with the above-mentioned photopolymerization initiator [E], 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. The filter coloring composition has high sensitivity. 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, ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate) ), Dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s- Examples include triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine.
These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

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 [A].
By using 0.05 part by weight or more of polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<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 colored composition 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. In general, the leveling agent content is preferably 0.003 to 1.0 part by weight with respect to 100 parts 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.

<Ultraviolet absorber, polymerization inhibitor>
The coloring composition for a color filter of the present invention can contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, etc. Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazoles such as 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4- Benzophenone series such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, salicylate series such as phenyl salicylate, p-tert-butylphenyl salicylate, Cyanoacrylates such as ethyl-2-cyano-3,3′-diphenylacrylate, 2,2,6,6, -tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis (2, 2,6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] And hindered amines such as [(2,2,6,6-tetramethyl-4-piperidinyl) imino].
These ultraviolet absorbers can be used singly or in combination of two or more at any ratio as required.

Examples of the polymerization inhibitor include hydroquinone such as methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol. Derivatives and phenolic compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. And manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine Nitroso compounds and their ammonium salts or aluminum salts and the like.
These polymerization inhibitors can be used singly or as a mixture of two or more at any ratio as required.

The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, with respect to 100 parts by weight of the colorant [A] in the coloring composition. .
By using 0.01 part by weight or more of the ultraviolet absorber or the polymerization inhibitor, better resolution can be obtained.

<Antioxidant>
The colored composition for a color filter of the present invention can contain an antioxidant in order to increase the transmittance of the coating film. The antioxidant is used to prevent the photopolymerization initiator [E] and the isocyanurate compound [C] contained in the color filter coloring composition from being oxidized and yellowed by a thermal process during thermal curing or ITO annealing. The transmittance of the coating film can be increased. 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.

Preferable antioxidants include hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, sulfide antioxidants, and the like. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.
These antioxidants can be used singly or in combination of two or more at any ratio as required.

  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) and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5- And di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

  In the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N , N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4- Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3,4 -Butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6- Tetramethyl-4-piperidyl) Mino} 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) -4 Polycondensate with -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 and the like.

  As the phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2- Yl) oxy] ethyl] amine and ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl).

  As sulfide-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.

The content of the antioxidant is preferably used in an amount of 0.1 to 5% by weight in a total of 100% by weight of the solid content of the color filter coloring composition.
When the amount of the antioxidant is less than 0.1% by weight, the effect of increasing the transmittance is small, and when it is more than 5% by weight, the hardness is greatly lowered, and the sensitivity of the coloring composition for the color filter is greatly decreased.

<Other ingredients>
The coloring composition for a color filter of the present invention contains an adhesion improver such as a silane coupling agent or an amine compound that has a function of reducing dissolved oxygen in order to improve adhesion to a transparent substrate. Can be made.

  Examples of the silane coupling agent include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, 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-amino Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Examples include aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The silane coupling agent 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 [A] in the coloring composition.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-ethylhexyl dimethylaminobenzoate, N, N-dimethyl paratoluidine, etc. are mentioned.

<The manufacturing method of the coloring composition for color filters>
The coloring composition for a color filter of the present invention is a dispersion of a colorant [A] in a pigment carrier such as a binder resin [B] and / or a solvent such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. In this case, a pigment dispersion is produced by finely dispersing by means of a photopolymerization initiator [E], binder resin [B], polyfunctional monomer [D], isocyanurate compound [C], Depending on the case, a sensitizer, a polyfunctional thiol, an ultraviolet absorber, a polymerization inhibitor, a storage stabilizer, a solvent, and other components can be mixed and stirred. The coloring composition for a color filter containing two or more pigments is prepared by mixing each pigment dispersion separately finely in a dye carrier and / or a solvent, and further mixing a photopolymerization initiator [E] or Polyfunctional monomer [D] and the like may be mixed and stirred. The isocyanurate compound [C] can obtain the same effect whether it is used in producing the pigment dispersion or added to the pigment dispersion later.

When the colorant [A] is dispersed in the binder resin [B] and / or the solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. The dispersion aid is excellent in dispersion of the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, the color composition for a color filter is obtained by dispersing the pigment in a resin and / or solvent using the dispersion aid. When an object is used, a color filter excellent in transparency can be obtained.
The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the pigment in the colorant [A].

  The coloring composition for the color filter 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.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a filter segment and / or a black matrix formed from the coloring composition for a color filter of the present invention on a transparent substrate, and the general color filter is a black matrix, at least 1 One red filter segment, at least one green filter segment, and at least one blue filter segment, or a black matrix, at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment It comprises.

  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. 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.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, chromium, a 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. However, the present invention is not limited thereto, and the coloring composition for color filters of the present invention A black matrix formed from is preferable. 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 and / or the black matrix on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  The dry film thickness of the filter segment and the black matrix is preferably 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.

  Formation of each color filter segment and black matrix 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 dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It is applied so that the film thickness is 0.2 to 10 μm. 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.

  Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove uncured portions and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by development, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

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.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase UV exposure sensitivity, after applying and drying the above color filter coloring composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. Ultraviolet exposure can also be performed after forming a film.

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

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

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

  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. In addition, the specific surface area of the pigment, the average primary particle diameter of the pigment, the weight average molecular weight (Mw) of the resin, the acid value of the resin, the heat resistance of the coating film, and the NMP resistance of the coating film (change in chromaticity, coating) The test method of film swelling and coating crack resistance is as follows.

<Specific surface area of pigment>
The specific surface area of the pigment was measured by an automatic vapor adsorption amount measuring apparatus (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) using the nitrogen adsorption BET method.

<Average primary particle diameter of pigment>
A solvent (for example, propylene glycol monomethyl ether acetate) is added to the pigment powder, and a small amount of a dispersant (for example, DIsperbyk-161: Big Chemie's dispersant) is added, and the sample for measurement is prepared by ultrasonic treatment for 1 minute. Next, using a transmission (TEM) electron microscope, three photographs (for three fields of view) in which primary particles of 100 or more pigments can be confirmed are prepared, and the sizes of the 100 primary particles are measured sequentially from the upper left. . Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment are measured in nm units, the average is the primary particle diameter of the pigment particles, and a total of 300 distributions are created in increments of 5 nm. The median value in increments of 5 nm (for example, 8 nm in the case of 6 nm or more and 10 nm or less) is approximated as the particle diameter of those particles, and the number average particle diameter is calculated by calculating based on each particle diameter and the number thereof.

<Resin polymerization average molecular weight (Mw)>
Polymerization average molecular weight (Mw) of the acrylic resin was converted to polystyrene using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. The weight average molecular weight (Mw).

<Resin acid value>
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the resin solution and stirred to dissolve uniformly, and an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) is used with a 0.1 mol / L KOH aqueous solution as a titrant. ) 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 of heat resistance test for coating film>
A coloring composition for a color filter is applied on a transparent substrate so that the dried coating film has a thickness of about 2.5 μm, and ultraviolet exposure is performed through a mask having a predetermined pattern. Thereafter, the film is dipped in a solvent or an alkali developer or sprayed with a developer or the like to remove uncured portions to form a desired pattern. Then, after heating in an oven at 230 ° C. for 1 hour and allowing to cool, the color difference 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source was measured with a microspectrophotometer ( Measurement was performed using “OSP-SP200” manufactured by Olympus Optical Co., Ltd. Then, as a heat resistance test, it was heated in an oven at 230 ° C. for 1 hour, and a color difference 2 (L * (2), a * (2), b * (2)) with a C light source was measured.
Using the measured color difference value, the color difference change rate ΔEab * was calculated by the following formula.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

<NMP resistance (color change, swelling of coating film, crack resistance of coating film) test method>
The coloring composition for a color filter was applied onto a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater to form a coating film having a thickness of 2.0 μm. Next, after pre-baking at 70 ° C. for 20 minutes, UV exposure was performed using a super high pressure mercury lamp through a mask that exposes a stripe pattern at a saturated exposure amount of +100 mJ / cm ² . After the exposure, development was performed with an alkaline developer for 90 seconds to form each color filter segment in a stripe shape on the substrate. The developed substrate was heat-treated at 230 ° C. for 60 minutes. After immersing a part of the substrate in N-methylpyrrolidone (NMP) for 5 minutes, the chromaticity before and after immersion was measured with a microspectrophotometer (trade name OSP-SP100: Olympus Optical Co., Ltd.) using a C light source. The degree change ΔE was calculated. Moreover, the film thickness before and behind immersion was measured with the surface shape measuring apparatus (Brand name DEKTAK8: ULVAC, Inc.), and the swelling rate was computed by the following formula.
[Swelling ratio] = ([film thickness after immersion] − [film thickness before immersion]) / [film thickness before immersion] × 100 (%)
Furthermore, the state (crack resistance) of the pattern surface was observed with an optical microscope, and the state of the pattern surface was observed to change.

<Method of coating film foreign matter test>
A test substrate was prepared from the colored composition immediately after preparation and evaluated by counting the number of particles. First, a coloring composition was applied on a transparent substrate so that the dried coating film was about 2.0 μm, and heated in an oven at 230 ° C. for 20 minutes to obtain a test substrate. Thereafter, surface observation is performed using a metal microscope “BX60” manufactured by Olympus System (magnification is 500 times), and the number of particles that can be observed in any five visual fields by transmission is counted.

  Prior to the examples, a method for producing a micronized pigment, a method for preparing a pigment dispersant solution, and a method for producing a pigment dispersion containing the coloring material A will be described.

<Method for producing acrylic resin solution>
(Acrylic resin solution (B-1))
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 70.0 parts of propylene glycol monoethyl ether acetate, heated to 80 ° C., and the reaction vessel was filled with nitrogen. After the substitution, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) )) A mixture of 7.4 parts and 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% by weight and a weight average molecular weight of 26000.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether acetate was added to obtain an acrylic resin solution (B-1) which is an alkali-soluble resin.

(Acrylic resin solution (B-2))
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was dropped over 2.5 hours from the dropping tube at a temperature to polymerize. Reaction was performed.
Next, the inside of the flask was purged with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours. The reaction was terminated when it reached 0.8, and a resin solution having a weight average molecular weight of about 12000 (measured by GPC) was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours. Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 30%, and ethylenically unsaturated active double An acrylic resin solution (B-2) which is an energy ray curable resin having a bond was obtained.
<Method for Producing Salt-Forming Compound (A)>
(Salt-forming compound (A-1))
In the following procedure, C.I. I. A salt-forming compound (A-1) consisting of Acid Red 52 and distearyldimethylammonium chloride (Coatamine D86P) (the molecular weight of the cation moiety was 550) was produced.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 52 is dissolved, sufficiently mixed and stirred, heated to 70 to 90 ° C., and then Cotamine D86P is added dropwise little by little. Coatamine D86P may be dissolved in water and used as an aqueous solution. After adding Cotamine D86P dropwise, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of Acid Red 52 and distearyldimethylammonium chloride, a salt-forming compound (A-1) was obtained.

(Salt-forming compound (A-2))
In the following procedure, C.I. I. A salt-forming compound (A-2) composed of Acid Red 52 and dilauryldimethylammonium chloride (the molecular weight of the cation moiety was 382) was produced.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 52 is dissolved, thoroughly mixed and stirred, heated to 70-90 ° C., and dilauryldimethylammonium chloride is then added dropwise little by little. Dilauryldimethylammonium chloride may be dissolved in water and used as an aqueous solution. After dropwise addition of dilauryldimethylammonium chloride, the mixture is stirred at 70 to 90 ° C. for 60 minutes and sufficiently reacted. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of acid red 52 and dilauryldimethylammonium chloride, a salt-forming compound (A-2) was obtained.

(Salt-forming compound (A-3))
In the following procedure, C.I. I. A salt-forming compound (A-3) consisting of Acid Red 52 and tristearyl monomethylammonium chloride (the molecular weight of the cation moiety was 788) was produced.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 52 is dissolved, sufficiently mixed and stirred, heated to 70 to 90 ° C., and then tristearyl monomethyl ammonium chloride is added dropwise little by little. Tristearyl monomethylammonium chloride may be dissolved in water and used as an aqueous solution. After dropwise addition of tristearyl monomethylammonium chloride, the mixture is stirred at 70 to 90 ° C. for 60 minutes and sufficiently reacted. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of acid red 52 and tristearyl monomethylammonium chloride, a salt-forming compound (A-3) was obtained.

(Salt-forming compound (A-4))
In the following procedure, C.I. I. A salt-forming compound (A-4) composed of Acid Red 289 and distearyldimethylammonium chloride (Cotamine D86P) (the molecular weight of the cation moiety was 550) was produced.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 289 is dissolved, thoroughly mixed and stirred, heated to 70-90 ° C., and then Cotamine D86P is added dropwise little by little. Coatamine D86P may be dissolved in water and used as an aqueous solution. After adding Cotamine D86P dropwise, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of Acid Red 289 and distearyldimethylammonium chloride, a salt-forming compound (A-4) was obtained.

(Salt-forming compound (A-5))
In the following procedure, C.I. I. A salt-forming compound (A-5) consisting of Acid Red 87 and distearyldimethylammonium chloride (Coatamine D86P) (the molecular weight of the cation moiety was 550) was produced.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 87 is dissolved, mixed and stirred thoroughly, heated to 70 to 90 ° C., and then Cotamine D86P is added dropwise little by little. Coatamine D86P may be dissolved in water and used as an aqueous solution. After adding Cotamine D86P dropwise, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of Acid Red 87 and distearyldimethylammonium chloride, a salt-forming compound (A-5) was obtained.

<Manufacture of refined pigments>
(Red refined pigment (PR-1))
Red pigment C.I. I. Pigment Red 254 (PR254) ("Irga Fore Red B-CF" manufactured by Ciba Japan), 8 parts of a pigment derivative of the formula (5), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were added to a 1 gallon kneader made of stainless steel ( And kneaded at 60 ° C. for 10 hours. Next, the mixture is poured into 3 liters of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and solvent, and then 80 It was dried for 1 day at 0 ° C. to obtain a red refined pigment (PR-2). The average primary particle diameter of the obtained pigment was 35 nm.

Formula (5)

(Red refined pigment (PR-2))
Red pigment C.I. I. Pigment Red 177 (PR177) (“Chromophthalred A2B” manufactured by Ciba Japan), 3500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 120 ° C. for 8 hours. Kneaded. 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. As a result, a red-refined pigment (PR-1) was obtained. The average primary particle diameter of the obtained pigment was 30 nm.

(Red refined pigment (PR-3))
Red pigment C.I. I. 100 parts of Pigment Red 242 (PR242) (“Novopalm Scarlet 4RF” manufactured by Clariant), 8 parts of a pigment derivative (D1), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho). And kneading at 60 ° C. for 10 hours. Next, the mixture is poured into 3 liters of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and solvent, and then 80 It was dried for 1 day at 0 ° C. to obtain a red salt milling pigment (PR-3). The average primary particle size of the obtained pigment was 32 nm.

(Green refined pigment (PG-1))
Green pigment C.I. I. 500 parts of Pigment Green 36 (PG36) (“Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), 8 at 120 ° C. Kneaded for 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. As a result, a green refined pigment (PG-1) was obtained. The average primary particle diameter of the obtained pigment was 32 nm.

(Green refined pigment (PG-2))
Green pigment C.I. I. 500 parts of Pigment Green 58 (PG58) (“First Gain Green A110” manufactured by DIC Corporation), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) at 120 ° C. for 8 hours. Kneaded. 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. As a result, a green refined pigment (PG-2) was obtained. The obtained pigment had a volume average primary particle size of 25 nm.

(Blue refined pigment (PB-1))
Blue pigment C.I. I. Pigment Blue 15: 6 (PB15: 6) (“Rionol Blue ES” manufactured by Toyo Ink Manufacturing Co., Ltd.) 500 parts, 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 120 ° C. for 12 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. As a result, a blue refined pigment (PB-1) was obtained. The obtained pigment had a volume average primary particle size of 25 nm.

(Yellow refined pigment (PY-1))
Quinophthalone yellow pigment C.I. I. 500 parts of Pigment Yellow 138 (PY138) ("Pariotol Yellow K0960-HD" manufactured by BASF), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 100 ° C. Kneaded for 6 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. As a result, a yellow refined pigment (PY-1) was obtained. The average primary particle diameter of the obtained pigment was 26 nm.

(Yellow refined pigment (PY-2))
Metal complex yellow pigment C.I. I. 500 parts of Pigment Yellow 150 (PY150) (LANXESS "E4GN"), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C for 6 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. As a result, a yellow refined pigment (PY-2) was obtained. The average primary particle diameter of the obtained pigment was 28 nm.

(Yellow refined pigment (PY-3))
Yellow pigment C.I. I. Pigment Yellow 139 (PY139) ("Irgafore Yellow 2R-CF" manufactured by Ciba Japan), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 100 ° C. Kneaded for 6 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. As a result, a yellow refined pigment (PY-3) was obtained. The average primary particle diameter of the obtained pigment was 36 nm.

(Purple refinement treatment pigment (PV-1))
Dioxazine-based purple pigment C.I. I. 500 parts of Pigment Violet 23 (PV23) (“Fast Violet RL” manufactured by Clariant), 2500 parts of sodium chloride, and 250 parts of polyethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 120 ° C. for 12 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 all day and night, and obtained the purple refinement | purification processing pigment (PV-1). The average primary particle diameter of the obtained pigment was 30 nm.

  Table 1 summarizes the average primary particle diameters of the respective color-reduced pigments produced.

<Method for adjusting pigment dispersant solution (X-1)>
A pigment dispersant (“Ajisper PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.) was diluted with propylene glycol monomethyl ether acetate to prepare a pigment dispersant solution (X-1) having a nonvolatile content of 30% by weight.

<Method for producing pigment dispersion>
(Pigment dispersion (P-R1))
16.0 parts of red micronized pigment (PR-1), 30.0 parts of acrylic resin solution (B-1), 5 parts of resin-type dispersant solution (X-1), 49 parts of ethylene glycol monomethyl ether acetate After stirring and mixing uniformly, using zirconia beads having a diameter of 0.5 mm, the mixture was dispersed for 3 hours in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), filtered through a 5 μm filter, and a PR254 pigment. A dispersion (P-R1) was obtained.

(Pigment dispersion (P-R2))
The PR177 pigment dispersion (P-) was prepared in the same manner as the pigment dispersion (P-R1), except that the red refinement-treated pigment (PR-1) was changed to the red refinement-treated pigment (PR-2). R2) was prepared.

(Pigment dispersion (P-R3))
The PR242 pigment dispersion (P-) was prepared in the same manner as the pigment dispersion (P-R1) except that the red refinement-treated pigment (PR-1) was changed to the red refinement-treated pigment (PR-3). R3) was prepared.

(Pigment dispersion (P-G1))
The pigment dispersion of PG36 (P--) was prepared in the same manner as the pigment dispersion (P-R1) except that the red refinement-treated pigment (PR-1) was changed to the green refinement-treated pigment (PG-1). G1) was prepared.

(Pigment dispersion (P-G2))
The pigment dispersion of PG58 (P-) was prepared in the same manner as the pigment dispersion (P-R1) except that the red refinement-treated pigment (PR-1) was changed to the green refinement-treated pigment (PG-2). G2) was prepared.

(Pigment dispersion (P-B1))
A PB15: 6 pigment dispersion (PB15: 6) was prepared in the same manner as the pigment dispersion (P-R1), except that the red refined pigment (PR-1) was changed to the blue refined pigment (PB-1). P-B1) was prepared.

(Pigment dispersion (P-Y1))
A pigment dispersion (P-138) of PY138 was prepared by the same production method as that of the pigment dispersion (P-R1) except that the red refinement treatment pigment (PR-1) was changed to a yellow refinement treatment pigment (PY-1). Y1) was prepared.

(Pigment dispersion (P-Y2))
The pigment dispersion (P-150) of PY150 is the same as the pigment dispersion (P-R1) except that the red refinement treatment pigment (PR-1) is changed to the yellow refinement treatment pigment (PY-2). Y2) was prepared.

(Pigment dispersion (P-Y3))
A pigment dispersion (P-139) of PY139 was prepared by the same production method as that of the pigment dispersion (P-R1) except that the red refinement treatment pigment (PR-1) was changed to a yellow refinement treatment pigment (PY-3). Y3) was prepared.

(Pigment dispersion (P-V1)
The PV23 pigment dispersion (P--) was prepared in the same manner as the pigment dispersion (P-R1) except that the red refinement-treated pigment (PR-1) was changed to the purple refinement-treated pigment (PV-1). V1) was prepared.

<Method for producing salt-forming compound-containing resin solution and xanthene-based compound-containing resin solution>
(Preparation of salt-forming compound-containing resin solution (DA-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a salt-forming compound-containing resin solution (DA-1).
Salt-forming compound (A-1): 20.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 80.0 parts

(Preparation of salt-forming compound-containing resin solution (DA-2 to 6))
Hereinafter, except that the salt-forming compound (A-1) was changed to the salt-forming compound (A) or xanthene compound shown in Table 2, the same procedures as in the salt-forming compound-containing resin solution (DA-1) were performed. Salt compound-containing resin solutions (DA-2 to 6) were prepared.

<Isocyanurate compound>

[Examples 1 to 58, Comparative Examples 1 to 36]
The types and parts by weight of the materials described in Tables 4 to 15 were mixed to prepare colored compositions 1 to 94 for color filters.

Abbreviations in Table 4 to Table 15 are shown below.
<Polyfunctional monomer [D]>
Polyfunctional monomer (D-1): Dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Multifunctional monomer (D-2): Trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Multifunctional monomer (D1): Carboxyl group-containing polyfunctional monomer TO-2349 (Toagosei Co., Ltd.), which is a mixture of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate and a succinic acid derivative of dipentaerythritol pentaacrylate Product, acid value: 68)

<Photopolymerization initiator [E]>
Photopolymerization initiator (E-1): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“Irgacure 907” manufactured by Ciba Japan)
Photopolymerization initiator (E-2): ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime)
("Irgacure OXE02" manufactured by Ciba Japan)

<Solvent>
Solvent (F-1): Cyclohexanone solvent (F-2): Propylene glycol monomethyl ether acetate solvent (F-3): Ethyl 3-ethoxypropionate

<Leveling agent>
Leveling agent (G-1): Dimethylsiloxane (“BYK-333” manufactured by Big Chemie)
Leveling agent (G-2): Dimethylsiloxane (“FZ-2” manufactured by Toray Dow Corning)

<Sensitizer>
Sensitizer (H-1): 2,4-diethylthioxanthone (“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Sensitizer (H-2):

<Multifunctional thiol>
Multifunctional thiol (I-1): trimethylolpropane tri (3-mercaptobutyrate)
("TPMB" manufactured by Showa Denko KK)
Multifunctional thiol (I-2): Trimethylolethanetri (3-mercaptobutyrate)
("TEMB" manufactured by Showa Denko KK)

<Ultraviolet absorber>
Ultraviolet absorber (J-1): 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazine
("TINUVIN400" manufactured by Ciba Japan)
Ultraviolet absorber (J-2): 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol
("TINUVIN900" manufactured by Ciba Japan)

<Polymerization inhibitor>
Polymerization inhibitor (K-1): N-nitrosophenylhydroxylamine aluminum salt ("Q-1301" manufactured by Wako Pure Chemical Industries, Ltd.)

<Antioxidant>
Antioxidant (L-1): Hindered phenol antioxidant 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)
Antioxidant (L-2): Hindered amine antioxidant bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate

<Melamine compound>
Melamine compound (M-1): (Nippon Carbide Industries Co., Ltd. “Nicarac MW-30”)

<UV curable isocyanurate monomer>
UV curable isocyanurate monomer (N-1): monoallyl diglycidyl isocyanurate (“MA-DGIC”, Shikoku Chemicals Co., Ltd.)
UV curable isocyanurate monomer (N-2): Dinoallyl monoglycidyl isocyanurate (Shikoku Kasei Kogyo Co., Ltd. “DA-MGIC”)

[Evaluation result of coloring composition]
Table 15 shows the results obtained by measuring the obtained colored compositions 1 to 87 based on the heat resistance test method, the NMP resistance (chromaticity change), and the test method related to the coating film foreign matter.
In the heat resistance test, ΔEab * is preferably 0 or more and less than 3, and more preferably 0 or more and less than 2.
The chromaticity change ΔEab * before and after NMP immersion is preferably 0 or more and less than 3, and more preferably 0 or more and less than 2. The swelling rate is preferably less than 3%, more preferably less than 2%.
In the coating film foreign matter test evaluation results, ◎ and ○ are good because the number of foreign matters is small, △ is a level where there is a large number of foreign matters but there is no problem in use, and × is used because uneven coating due to foreign matter occurs. This is equivalent to a state where it is not possible.
: Less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or more

  As shown in Tables 15 and 16, the color filter coloring composition of the present invention containing the isocyanurate compound [C] has a heat resistance of ΔEab * 3 or less, and introduces an epoxy group of a certain level or more for NMP resistance. As a result, it was within ΔEab * 3 or less and exhibited excellent performance. Also, the solubility in the solvent was sufficiently soluble in the solvent by introducing an alkyl chain, and the generation of foreign matter could be suppressed.

  On the other hand, the coloring composition for the color filter of the comparative example had good solubility in a solvent for those not containing the isocyanurate compound [C] and the system into which the melamine compound was introduced, but the heat resistance ΔEab * was 3 In addition, ΔEab * exceeded 3 in NMP resistance. In addition, in the system using an isocyanurate compound having three epoxy groups in one molecule alone, the heat resistance and NMP resistance became ΔEab * 3 or less, but due to poor solubility, Foreign matter was generated. In addition, for systems using an isocyanurate compound containing an epoxy group and a UV curable double bond in one molecule, the heat resistant color difference ΔEab * is alkyl-modified due to the effect of the double bond remaining during thermal curing. It became worse compared to things.

(Manufacture of color filters)
A black colored composition was applied to a thickness of about 1.0 μm on a 100 mm × 100 mm glass substrate with a die coater, and the solvent was removed and dried in an oven at 70 ° C. for 20 minutes. Subsequently, stripe pattern exposure was performed with ultraviolet rays using an exposure apparatus. The exposure amount was 100 mJ / cm ² . Furthermore, after spray development with a developer composed of an aqueous sodium carbonate solution to remove unexposed portions, the substrate was washed with ion-exchanged water, and this substrate was heated at 230 ° C. for 20 minutes to form a black matrix having a line width of about 10 μm. .

Next, a colored composition 13 as a red colored composition was applied to a thickness of about 2 μm on a glass substrate on which a black matrix was formed, and the solvent was removed and dried in an oven at 70 ° C. for 20 minutes. Subsequently, stripe pattern exposure was performed with ultraviolet rays using an exposure apparatus. The exposure amount was 100 mJ / cm ² . Furthermore, after spray development with a developer composed of an aqueous sodium carbonate solution to remove unexposed portions, the substrate is washed with ion-exchanged water, and this substrate is heated at 230 ° C. for 30 minutes to form a red filter segment having a line width of about 50 μm. did. Then, in the same manner, a green filter segment is formed using a coloring composition 37 that is a green coloring composition next to a red filter segment, and then a blue filter segment is formed using a coloring composition 39 that is a blue coloring composition. Then, a color filter having three color filter segments on the same glass substrate was obtained.
When the colored composition for color filter in the present invention is used, it is possible to produce a color filter having a filter segment having good NMP resistance (chromaticity change, coating film swelling, coating film crack resistance) and heat resistance. It was.

Claims (7)

A coloring composition for a color filter, comprising at least a coloring agent [A], a resin [B], and a compound [C] represented by the general formula (1).

[In General Formula (1), each R ₁ is independently a group represented by General Formula (2) or General Formula (3), but at least one is represented by General Formula (3) Is the group]

[In General Formula (3), R ₂ is an optionally substituted alkyl group having 1 to 20 carbon atoms. R ₃ is a hydrogen atom or a group represented by the general formula (4)]

[In General Formula (4), R ₄ is an optionally substituted alkyl group having 1 to 20 carbon atoms]
Compound [C] represented by general formula (1) is a compound in which two of R ₁ are groups represented by general formula (2) and the other is a group represented by general formula (3) The coloring composition for a color filter according to claim 1, comprising:
Compound [C] represented by the general formula (1) is a compound in which one of R ₁ is a group represented by the general formula (2) and the remaining two are groups represented by the general formula (3). The coloring composition for color filters according to claim 1, wherein the coloring composition is contained.
Further, R ₁ is any general formula (3) contains a compound which is a group represented by a color filter for coloring composition according to any of claims 1 to 3, wherein in formula (1) .
Furthermore, polyfunctional monomer [D] and / or photoinitiator [E] are contained, The coloring composition for color filters in any one of Claims 1-4 characterized by the above-mentioned.
The coloring composition for a color filter according to any one of claims 1 to 5, wherein the colorant [A] contains a dye or a salt-forming compound thereof [A1].
  The color filter formed by shape | molding the coloring composition for color filters in any one of Claims 1-6.