JP2013156499A - Colored composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition for a color filter having high brightness even when it is subjected to heat treatment under 230°C or more in a color filter formation process, and a color filter having high brightness formed using the colored composition for a color filter.SOLUTION: A colored composition for a color filter includes a colorant [A] including a xanthene dye [A1], a binder resin [B], an antioxidant [C] or a melamine compound [D]. A color filter includes a filter segment formed of the colored composition for a color filter, on a substrate.

Description

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

In the liquid crystal display device, a liquid crystal material and a pixel are interposed between two polarizing plates, a voltage is applied to each pixel to change the alignment state of the liquid crystal material, and the degree of polarization of light passing through the first polarizing plate is changed. It is a display device that changes and controls the transmitted light passing through the second polarizing plate to display the screen.
By providing a color filter between the two polarizing plates, color display becomes possible, and it has come to be used for televisions, personal computers, monitors and the like.

  The color filter is provided with a grid-like light-shielding film black matrix (hereinafter referred to as BM) for the purpose of preventing color mixture of transmitted light and increasing display contrast on a transparent substrate such as a glass plate, and then a plurality of colors (usually red, Green and blue) filter segments are provided. The filter segments are as fine as several microns to several hundreds of microns, and the filter segments are arranged in the form of fine bands (stripes) of two or more different hues (stripe arrangement), or are arranged vertically and horizontally. (Delta arrangement) etc. The filter segment and the BM are formed by drying at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. by applying a coloring composition.

  In a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. 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.

The quality required for color liquid crystal display devices includes high image quality and low power consumption.
In order to achieve these, color filters with high brightness, high contrast, and high resolution are required.
In particular, in recent years, from the viewpoint of power consumption, the brightness of color filters has been increasing.
When a color filter with high brightness is used, the light transmittance is high, so that the number of backlights that are light sources can be reduced and power consumption can be reduced.

  Conventional color filters have been able to achieve high brightness and a wide color display area by combining a blue filter segment with a copper phthalocyanine pigment and a dioxazine pigment. However, as described above, higher brightness is required for the color filter.

  A xanthene dye is known as a dye exhibiting a magenta color. In particular, the spectrum of xanthene dyes has a high transmittance in the vicinity of 425 to 500 nm when compared with blue pigments such as copper phthalocyanine pigments and cyanine pigments. When a segment is produced, it has been proposed that a blue filter segment with higher brightness can be obtained. (For example, see Patent Documents 1 and 2)

  However, when a pixel containing the xanthene dye was prepared and the chromaticity was measured, the brightness was lowered by 230 ° C. high temperature drying at the time of pixel formation compared to before high temperature drying. The decrease in brightness is very large compared to pixels made only with pigment systems. This is presumably because the xanthene dyes formed aggregates by heat treatment, and the aggregates broadened the spectral curve, resulting in a decrease in brightness. Furthermore, if the coloring composition increases the components such as the photopolymerization initiator and the photopolymerizable monomer in order to enhance the photocurability, yellowing occurs in the post-bake process at 230 ° C. or more, and the brightness is lowered. There is also a problem that it ends up.

JP 2009-265641 A JP 2010-32999 A

  An object of the present invention is to provide a high brightness color filter coloring composition that can withstand a heat treatment of 230 ° C. or more during color filter formation, and a high brightness color filter formed using the color filter coloring composition. Is to provide.

  As a result of intensive studies, the present inventors, as a result of containing a xanthene dye [A1] and an antioxidant [C] or a melamine compound [D], have excellent heat resistance and high brightness. The inventors have found that a colored composition for a filter can be obtained, and have reached the present invention.

  That is, the present invention relates to a color filter coloring composition comprising a colorant [A] containing a xanthene dye [A1], a binder resin [B], and an antioxidant [C].

  That is, the present invention relates to a color filter coloring composition comprising a colorant [A] containing a xanthene dye [A1], a binder resin [B], and a melamine compound [D].

  The present invention also relates to the color composition for a color filter, wherein the xanthene dye [A1] is a salt forming compound of a xanthene acid dye and / or a sulfonic acid amide compound of a xanthene acid dye.

  In the present invention, the antioxidant [C] is at least one antioxidant selected from the group consisting of a hindered phenol antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. It is related with the said coloring composition for color filters characterized by the above-mentioned.

  In the color filter, the content of the antioxidant [C] is 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition. The present invention relates to a coloring composition.

  The color filter coloring according to claim 5 or 6, wherein the content of the melamine compound [D] is 2 to 30 parts by weight with respect to 100 parts by weight of the colorant [A]. Composition.

  In addition, the present invention relates to the coloring composition for a color filter, which further contains a polyfunctional monomer [E] and / or a photopolymerization initiator [F].

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

  With the color filter coloring composition of the present invention, even when heat treatment at 230 ° C. or higher is performed in the color filter forming step, a high brightness filter segment can be formed because of excellent heat resistance. Accordingly, a color liquid crystal display device with low power consumption can be manufactured using this color filter.

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]>
<< Xanthene dye [A1] >>
The colorant [A] of the present invention contains a 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 a xanthene acid dye.

  The xanthene dye [A1] 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 [A1], rhodamine dyes are preferable because they are excellent in color developability and resistance.

  Hereinafter, the form of the xanthene dye [A1] 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.

  The xanthene dye [A1] used in the present invention is, among others, a salt formation compound of a xanthene acid dye prepared by salting a xanthene acid dye with a quaternary ammonium salt or a sulfonamide of a xanthene acid dye. Since these are particularly preferred, these two forms will be described in detail below.

(Salt-forming compounds of xanthene acid dyes)
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.

-Salt-forming compound comprising xanthene acid dye and quaternary ammonium salt compound The xanthene dye [A1] used in the present invention should be used as a salt-forming compound comprising the above-mentioned xanthene acid dye and quaternary ammonium salt compound. Is most preferable from the viewpoints 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 (1). 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 (1) can be used as a quaternary ammonium salt compound.

[一般式（１）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。]

[In General Formula (1), 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 ^- is representative of 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. . (See Reference 1)
(Reference 1) Japanese Patent Application No. 2011-150752

Resin having a cationic group in the side chain The resin having a cationic group in the side chain is an alkaline resin containing a structural unit represented by the following general formula (2), and the cationic group in the general formula (2) However, a salt-forming compound can be obtained by forming a salt with the anionic group of the xanthene acid dye.

[In General Formula (2), R ₅ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{6 to} R ₈ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{6 to} R ₈ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₉ —, —COO—R ₉ —, and R ₉ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

-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.

  The salt-forming compound used in the present invention is prepared by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by the general formula (2) and a xanthene acid dye are dissolved, It can be easily obtained by mixing an aqueous solution of a resin having a cationic group in the side chain represented by the formula (2) and an aqueous solution of a xanthene acid dye under stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the xanthene acid dye are ionized, and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the resin and the counter cation of the xanthene-based acidic dye is water-soluble and can be removed by washing with water. The resin having a cationic group in the side chain to be used and the xanthene acid dye may be used alone or in a plurality of types having different structures.

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.

(Sulphonic acid amide compound of xanthene acid dye)
The xanthene-based acid dye in the present invention is preferably sulfonated to give a sulfonic acid amide compound because high heat resistance, light resistance, and solvent resistance can be imparted.
A sulfonic acid amide compound of a xanthene acid dye that can be preferably used for the xanthene dye [A1] 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.

《Other colorants》
When the colorant [A] of the coloring composition for color filter of the present invention is further used in combination with the blue pigment [A2], a spectral spectrum is observed at around 425 to 500 nm having characteristic peaks of many backlights. Can have a high transmittance, and higher brightness can be obtained as a blue filter segment than a colorant in which a conventional blue pigment and the following other pigments are combined.
Examples of the blue pigment [A2] 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.

Further, it can be used in combination with a pigment other than the blue pigment [A2].
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.

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.
Examples of orange pigments that work in the same way as red pigments include C.I. I. Orange pigments such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61 can be used. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment red 254, C.I. I. It is particularly preferable to use Pigment Red 177.

<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, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. -EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  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 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.

<Antioxidant [C]>
Examples of the antioxidant [C] include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
The coloring composition has a large absorption of the dye during pattern exposure, and it is difficult for light to pass through the inside. Therefore, it is common to increase sensitivity by increasing the amount of photopolymerization initiator and photopolymerization monomer, but at this time, excess components that were not used for pattern exposure are removed during the post-baking process. The problem arises that the radicals are generated by the heat of the heat and the yellowing occurs due to the formation of peroxides and the brightness is lowered.
Since the antioxidant (C) of the present invention can suppress the yellowing of the photopolymerization initiator and the polyfunctional monomer in such a post-bake process, the brightness does not decrease in the color filter forming process, and the luminance is reduced. High color filters can be formed.

  Antioxidant (C) has a primary antioxidant that suppresses generation of radicals by heat and a secondary antioxidant that decomposes peroxides generated by radicals, and a phenolic antioxidant is a primary antioxidant, Post-baking is required when a phenolic antioxidant is used in combination with a sulfurous antioxidant or a phosphorous antioxidant because the sulfurous antioxidant or phosphorus antioxidant has the function of a secondary antioxidant. It is more preferable because yellowing of the coating film in the process can be suppressed, and a filter segment with high brightness and high definition can be formed.

《Phenolic antioxidant》
The phenol-based antioxidant functions as a primary antioxidant that suppresses generation of radicals by heat.
Examples of the phenolic antioxidant contained in the photosensitive coloring composition of the present invention include 2,6-di-tert-butyl-4-ethylphenol and 2,4-bis- (n-octylthio) -6. -(4-Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis {3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate}, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl Ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2, 6-di-t-butyl-4-methoxyphenol, triethylene glycol-bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, pentaerythrityl-tetrakis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, octadecyl-3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) Benzene etc. are mentioned, You may use individually or 2 types or more.

  Among them, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate}, N, N ′ (-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t A hindered phenolic antioxidant selected from the group consisting of -butyl-4-hydroxybenzylphosphonate-diethyl ester and tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate is From the standpoint of balance between photocurability and lightness.

<Sulfur-based antioxidant or phosphorus-based antioxidant>
Sulfur-based antioxidants or phosphorus-based antioxidants act as secondary antioxidants that decompose peroxides generated by radicals.
(Sulfur-based antioxidant)
A sulfur-based antioxidant is an antioxidant containing sulfur in the molecule. As such a sulfur-containing antioxidant, commercially available ones can be used, but dioctadecyl 3,3′-thiodipropanoate, dimyristyl-3,3′-thiodipropionate, dipalmityl-3,3′- Thiodipropionate, distearyl-3,3′-thiodipropionate, 4,4′-thiobis-3-methyl-6-tert-butylphenol, thiodiethylenebis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], and is preferably at least one compound selected from the group consisting of these, and one or more of these may be used.

(Phosphorus antioxidant)
Although what is marketed can be used as phosphorus antioxidant, Tris [2,4-di- (tert) -butylphenyl] phosphinetris [2-[[2,4,8,10-tetrakis ( 1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-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, ethylbisphosphite (2,4-ditert-butyl-6-) It is preferable that it is at least one compound selected from the group consisting of these, and these may be used alone or in combination of two or more.

  When these antioxidants are used in combination, the content of the phenol-based antioxidant is based on the total content of the phenol-based antioxidant and the sulfur-based antioxidant or the phosphorus-based antioxidant (100% by weight). ) Is preferably 20 to 95% by weight, more preferably 45 to 95% by weight, and even more preferably 55 to 95% by weight. When the content of the phenolic antioxidant is less than 20% by weight, the effect of suppressing a decrease in lightness in the post-baking process is small, and when it is more than 95% by weight, the photocurability may be insufficient.

  The content of the antioxidant [C] in the photosensitive coloring composition of the present invention is preferably 0.1 to 10% by weight in 100% by weight of the solid content of the coloring composition, and preferably 0.5 to 5%. More preferably, it is% by weight. When the content of the antioxidant [C] is less than 0.1% by weight, the effect of suppressing the decrease in lightness in the post-baking process is small, and when it is more than 10% by weight, the photocurability may be insufficient. is there.

<Melamine compound [D]>
The melamine compound [D] of the present invention is a mixture of the melamine compound represented by the following general formula (3) and / or a partial condensate thereof (hereinafter sometimes abbreviated as melamine compound [D]). However, it is preferable because a minute colored film having low viscosity and stability at room temperature and excellent in various resistances can be formed by thermosetting.

［一般式（３）中、Ｄ₁、Ｄ₃、およびＤ₅はそれぞれ独立して、水素原子、メチロール基、−ＣＨ₂ＯＣＨ₃、または−ＣＨ₂ＯＣ₄Ｈ₉であり、Ｄ₂、Ｄ₄、およびＤ₆はそれぞれ独立して、メチロール基、−ＣＨ₂ＯＣＨ₃、または−ＣＨ₂ＯＣ₄Ｈ₉である。］

[In General Formula (3), D ₁ , D ₃ , and D ₅ are each independently a hydrogen atom, a methylol group, —CH ₂ OCH ₃ , or —CH ₂ OC ₄ H ₉ , and D ₂ , D ₄ and D ₆ are each independently a methylol group, —CH ₂ OCH ₃ , or —CH ₂ OC ₄ H ₉ . ]

Among these, when D _{1 to} D ₆ are all of a type having a methylolimino group (—NHCH ₂ OH) rather than a full ether type of —CH ₂ OCH ₃ , the reactivity is high and the heat resistance improving effect is excellent. Therefore, it is preferable.

Examples of the melamine compound [D] include the following commercially available products.
D _{1 to} D ₆ are full ether type (—CH ₂ OCH ₃ ) products such as Nicarak MW-30M, Nicarak MW-30, Nicarac MW-22, and Nicarac MW-21 (manufactured by Nippon Carbide Industries Co., Ltd.), and , Cymel 300, Cymel 301, Cymel 303, Cymel 350 (manufactured by Nippon Cytec Industries, Inc.), and the like.
Further, as a product of methylol imino type (—NHCH ₂ OH), Nicarak MS-001, Nicarax MX-002, Nicarak MX-750, Nicarax MX-706, Nicarak MX-042, Nicarac MX-035 (Nippon Carbide Industries Co., Ltd.) Manufactured).
The D ₁ to D ₆ is NIKALAC MS-11 and the like as a product of methylol type (-CH ₂ OH).
Nicalac MS-730 is an example of an imino type (—NHCH ₂ OR) product.

  The content of the melamine compound [D] is preferably 2 to 30 parts by weight with respect to 100 parts by weight of the colorant [A]. When the melamine compound [D] is less than 5 parts by weight, curability is insufficient. On the other hand, if the melamine compound [D] exceeds 70 parts by weight, the effect of film shrinkage due to condensation is great, and it is difficult to form a cured coating film.

<Polyfunctional monomer [E]>
As the polyfunctional monomer [E] used in the present invention, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate , Polyfunctional monomers [E1] having acidic groups, such as various acrylic esters and methacrylic esters such as propylene oxide-modified trimethylolpropane tri (meth) acrylate, or photopolymerizable monomers in which polymerization is partially induced by radicals Etc. can be raised.

(Polyfunctional monomer having an acidic group [E1])
As the polyfunctional monomer [E1] having an acidic group, for example, 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 [E] 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 [F]>
As the photopolymerization initiator [F], 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 [F] can be used singly or as a mixture of two or more at any ratio as required.

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

  These photopolymerization initiators [F] 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, based on 100 parts by weight of the colorant [A] 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 [F], 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.

<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 comprises a colorant [A] containing a xanthene dye [A1] in a dye carrier such as a binder resin [B] and / or a solvent, a three roll mill, a two roll mill, a sand mill, A colorant dispersion is produced by finely dispersing using various dispersing means such as a kneader and an attritor, and a binder resin [B], an antioxidant [C], and a melamine are added to the colorant dispersion as necessary. Compound [D], polyfunctional monomer [E], photopolymerization initiator [F], solvent, and in some cases sensitizer, polyfunctional thiol, UV absorber, polymerization inhibitor, storage stabilizer, and other components are mixed It can be produced by stirring.
In addition, when the solubility of the colorant [A] such as a dye is high, specifically, it is highly soluble in the solvent to be used. There is no need to manufacture in a dispersed manner.

  In addition, a color filter coloring composition containing two or more colorants is prepared by mixing finely dispersed colorant dispersions in a colorant carrier and / or a solvent, and further mixing a photopolymerization initiator [ F], polyfunctional monomer [E] and the like may be mixed and stirred. The antioxidant [C] and the melamine compound [D] can be used in the production of the colorant dispersion or can be added to the colorant dispersion later to obtain the same effect.

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 with respect to 100 parts by weight of the colorant [A].

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good. In addition, as the dispersion aid used in the present invention, those containing no halogen atom are preferable.

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

  The 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 colorant [A] from the viewpoint of improving dispersibility. is there. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

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

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 1300 manufactured by Nippon Lubrizol Co., Ltd., such as P104, P104S, 220S, 6919, 21116, 21324, 21407, 21715 or Lactimon, Lactimon-WS or Bykumen , 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095 , 55000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, manufactured by Ciba Japan 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 501 , 5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

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

  The 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 is provided with a filter segment and / or a black matrix formed on the substrate from the coloring composition for a color filter of the present invention, and a general color filter includes, for example, a black matrix, And red, green and blue filter segments. The filter segment may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  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.
Moreover, the average primary particle diameter of a pigment, the weight average molecular weight (Mw) of resin, and the measuring method of the ammonium salt value of resin which has a cationic group in a side chain are as follows.

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

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

(Ammonium salt value of a resin having a cationic group in the side chain)
The ammonium salt value of the resin having a cationic group in the side chain is a value converted to the equivalent of potassium hydroxide after being obtained by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator. Represents the ammonium salt value of the solid content.

  Subsequently, the binder resin solution, the resin for salt-forming dye, the xanthene dye [A1], the xanthene dye-containing solution, the fine pigment, and the pigment dispersion used in Examples and Comparative Examples will be described.

<Method for producing binder 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))
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobisisobutyronitrile 1.33 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution.
Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.
About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight, and the acrylic resin solution (B -2) was prepared. The weight average molecular weight (Mw) was 18000.

<Method for producing salt dye resin>
(Preparation of resin 1 having a cationic group in the side chain)
74.1 parts of isopropyl alcohol was charged into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 33.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride salt, and 15.6 parts of methyl ethyl ketone were homogenized. Thereafter, the mixture was placed in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain Resin 1 having a cationic group in the side chain whose resin component was 40% by weight. The ammonium salt value of the obtained resin was 33 mgKOH / g.

(Preparation of resin 2 having a cationic group in the side chain)
74.1 parts of isopropyl alcohol was charged into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 15.7 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride salt, 15.0 parts of hydroxyethyl methacrylate, methacrylic acid After 2.5 parts and 15.6 parts of methyl ethyl ketone were made uniform, they were charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain Resin 2 having a cationic group in the side chain whose resin component was 40% by weight. The ammonium salt value of the obtained resin was 33 mgKOH / g.

<Method for Producing Xanthene Dye [A1]>
(Salt-forming compound (A-1))
In the following procedure, C.I. I. A salt-forming compound (A-1) comprising Acid Red 52 and Resin 1 having a cationic group in the side chain was produced.
51 parts of vinyl-based resin 1 was added to 2000 parts of water, and after sufficient stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound (A-1) between acid red 52 and resin 1 having a cationic group in the side chain was obtained. At this time, C.I. in the salt-forming compound (A-1). I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

(Salt-forming compound (A-2))
In the following procedure, C.I. I. A salt-forming compound (A-2) comprising Acid Red 52 and Resin 2 having a cationic group in the side chain was produced.
51 parts of the resin 2 having a cationic group was added to 2000 parts of water, and after sufficiently stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound (A-2) between acid red 52 and resin 1 having a cationic group in the side chain was obtained. At this time, C.I. in the salt-forming compound (A-2). I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

(Salt-forming compound (A-3))
In the following procedure, C.I. I. A salt-forming compound (A-3) comprising Acid Red 289 and Resin 1 having a cationic group in the side chain was produced.
88 parts of the resin 1 having a cationic group in the side chain was added to 2000 parts of a 10% methanol aqueous solution, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts C.I. I. An aqueous solution in which Acid Red 289 was dissolved was prepared and added dropwise to the previous resin solution little by little. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto 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, and 43 parts of C.I. I. A salt-forming compound (A-3) between Acid Red 289 and Resin 1 having a cationic group in the side chain was obtained. At this time, C.I. in the salt-forming compound (A-3). I. The content of the effective pigment component derived from Acid Red 289 was 25% by weight.

(Salt-forming compound (A-4))
In the following procedure, C.I. I. A salt-forming compound (A-4) composed 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, mixed and stirred sufficiently, 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 (A-4) of acid red 52 and distearyldimethylammonium chloride was obtained. At this time, C.I. in the salt-forming compound (A-4). I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

(Salt-forming compound (A-5))
In the following procedure, C.I. I. A salt-forming compound (A-5) composed of Acid Red 52 and dialkyl (alkyl is C14 to C18) dimethylammonium chloride (Arcade 2HT-75) (the molecular weight of the cation moiety is 438 to 550) was prepared.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 52 is dissolved, mixed and stirred sufficiently, heated to 70 to 90 ° C., and then Arcard 2HT-75 is added dropwise little by little. Arcade 2HT-75 may be dissolved in water and used as an aqueous solution. After dropping Arcade 2HT-75, 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 (A5) of acid red 52 and dialkyl (alkyl is C14 to C18) dimethylammonium chloride was obtained. At this time, C.I. in the salt-forming compound (A-5). I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

(Salt-forming compound (A-6))
In the following procedure, C.I. I. A salt-forming compound (A-6) composed 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, 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 87 and distearyldimethylammonium chloride, a salt-forming compound (A-6) was obtained. At this time, C.I. in the salt-forming compound (A-6). I. The content of the effective pigment component derived from Acid Red 87 was 25% by weight.

(Sulphonic acid amide compound (A-7))
C. I. Acid Red 52 was converted to a sulfonyl chloride by a conventional method and then reacted with a theoretical equivalent of 2-ethylhexylamine in dioxane to obtain C.I. I. A sulfonic acid amide compound (A-7) of Acid Red 52 was obtained. (Based on the description of JP-A-6-194828.) At this time, C.I. I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

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

(Preparation of xanthene dye-containing solution (DA-2 to 6))
Hereinafter, except having changed the salt-forming compound (A-1) into the salt-forming compound shown in Table 1 or the sulfonic acid compound (A-2 to 7), the same as the colorant-containing resin solution (DA-1). Thus, xanthene dye-containing solutions (DA-2 to 7) were prepared.

The produced xanthene dye-containing solutions are summarized in Table 1.

<Production method of fine pigment>
(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 average primary particle diameter of the obtained pigment was 25 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.

<Method for preparing pigment dispersant solution>
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 having a nonvolatile content of 30% by weight.

<Method for producing pigment dispersion>
(Pigment dispersion (P-B1))
12.0 parts of blue refined pigment (PB-1), 32.5 parts of acrylic resin solution (B-1), 5 parts of pigment dispersant solution, and 50.5 parts of ethylene glycol monomethyl ether acetate are stirred and mixed uniformly. After that, using a zirconia bead having a diameter of 0.5 mm, it was dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), filtered through a 5 μm filter, and a PB15: 6 pigment dispersion. (P-B1) was obtained.

(Pigment dispersion (P-V1)
The PV23 pigment dispersion (P-) was prepared in the same manner as the pigment dispersion (P-B1) except that the blue refinement treatment pigment (PB-1) was changed to the purple refinement treatment pigment (PV-1). V1) was prepared.

[Example 1]
(Preparation of colored composition 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 colored composition 1.

Blue pigment dispersion (P-B1): 14.07 parts Xanthene dye-containing solution (DA-1): 3.62 parts Binder resin solution (B-1): 5.22 parts Photopolymerization initiator: 2.67 Part 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (“Irgacure 379” manufactured by Ciba Japan)
Sensitizer: 0.67 part 2,4-diethylthioxanthone (“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Polyfunctional monomer (E-1): 7.05 parts dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Antioxidant (C-1): 0.25 part phenolic antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Antioxidant (C-2): 0.16 parts phosphorus antioxidant tris [2,4-di- (tert) -butylphenyl] phosphine Solvent: 66.29 parts propylene glycol monomethyl ether acetate

[Examples 2 to 13, Comparative Examples 1 to 3]
(Preparation of colored compositions 2 to 16)
Hereinafter, the colored composition of Example 1 except that the pigment dispersion, the xanthene dye-containing solution, the binder resin solution, the polyfunctional monomer, and the antioxidant are changed to the types and blending amounts (parts by weight) shown in Table 2. In the same manner as in Example 1, colored compositions 2 to 16 were produced.

[Example 12]
(Preparation of colored composition 17)
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a colored composition 1.

Blue pigment dispersion (P-B1): 14.07 parts Xanthene dye-containing solution (DA-1): 3.62 parts Binder resin solution (B-1): 5.22 parts Photopolymerization initiator: 2.67 Part 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (“Irgacure 379” manufactured by Ciba Japan)
Sensitizer: 0.67 part 2,4-diethylthioxanthone (“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Polyfunctional monomer (E-1): 7.05 parts dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Melamine compound (D-1): 0.48 part (“Nikalak MS-11” manufactured by Nippon Carbide Industries Co., Ltd.)
Solvent: 66.29 parts propylene glycol monomethyl ether acetate

[Examples 13 to 24, Comparative Examples 4 to 7]
(Preparation of colored compositions 18 to 34)
Hereinafter, the coloring composition of Example 12 except that the pigment dispersion, the xanthene dye-containing solution, the binder resin solution, the polyfunctional monomer, and the melamine compound are changed to the types and blending amounts (parts by weight) shown in Tables 4-6. In the same manner as Product 17, colored compositions 18 to 34 were produced.

* Melamine compounds / colorants (parts)
: Content (parts by weight) of melamine compound [D] with respect to 100 parts by weight of colorant [A]

Abbreviations in Tables 2-6 are shown below.
<Antioxidant>
Antioxidant (C-1): phenolic antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Antioxidant (C-2): phosphorus Antioxidant Tris [2,4-di- (tert) -butylphenyl] phosphine / antioxidant (C-3): sulfur-based antioxidant 3,3′-dioctadecyl thiodipropanoate <photopolymerization initiator>
Photopolymerization initiator: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (“Irgacure 379” manufactured by Ciba Japan) )
<Sensitizer>
Sensitizer: 2,4-diethylthioxanthone (“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)

<Multifunctional monomer>
Polyfunctional monomer (E-1): Dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Multifunctional monomer (E-2): Succinic anhydride adduct of a mixture of a polyfunctional monomer pentaerythritol triacrylate having an acidic group and dipentaerythritol triacrylate (“Aronix M-520” manufactured by Toagosei Co., Ltd.)

<Melamine compound>
Melamine compound (D-1): Methylol imino type (“Nicarac MX-706” manufactured by Nippon Carbide Industries, Ltd.)
Melamine compound (D-2): imino type (“Nicarac MS-730” manufactured by Nippon Carbide Industries, Ltd.)
Melamine compound (D-3): Methylol type (“Nicarac MS-11” manufactured by Nippon Carbide Industries Co., Ltd.)
Melamine compound (D-4): Full ether type (“Nikalak MW-30” manufactured by Nippon Carbide Industries, Ltd.)

<Other cross-linking agents>
EX-611: Epoxy resin ("EX-611" manufactured by Nagase ChemteX Corporation)
<Solvent>
Solvent: Propylene glycol monomethyl ether acetate

[Evaluation of coloring composition]
The obtained colored composition was evaluated for brightness, heat resistance, chemical resistance, and sensitivity by the following methods. The results are shown in Tables 7 and 8.

<Lightness evaluation>
The obtained colored composition was applied on a glass substrate in a film thickness such that x = 0.141 and y = 0.084 using a C light source, and then exposed to ultraviolet light through a mask having a predetermined pattern. Thereafter, an alkali developer was sprayed by spraying to remove the uncured portion and form a desired pattern. About the obtained coating film, the brightness before and behind heat processing at 230 degreeC for 20 minutes was measured with the microspectrophotometer ("OSP-SP200" by Olympus Optical Co., Ltd.).
If the chromaticity shifts, create a colored composition with the ratio of the pigment dispersion and xanthene dye-containing solution appropriately changed, measure the chromaticity and draw a calibration curve to obtain the lightness at the desired chromaticity. Calculated.
In the evaluation results, ○ is good, Δ is a level that does not cause a problem in use, × corresponds to a state where it cannot be used, ○: 12.4 or more Δ: 12.0 or more, but less than 12.4 ×: 12 Less than .0

<Heat resistance evaluation>
The substrate obtained by lightness evaluation was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.) before and after heat treatment at 230 ° C for 60 minutes in an oven, and the difference from lightness before and after heat treatment at 230 ° C for 20 minutes It was measured. The rank of evaluation is as follows. In the evaluation results, ◯ is good, Δ is a level that does not cause a problem in use, and × corresponds to a state where it cannot be used.
○: Less than 0.4 Δ: 0.4 or more and less than 0.8 ×: 0.8 or more

<Chemical resistance evaluation>
The substrate obtained by the lightness evaluation was immersed in N-methyl-2-pyrrolidone at room temperature for 5 minutes, washed with running water for 1 minute, and then air-dried. The chromaticity of the obtained substrate was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.), and the difference (color difference) from the chromaticity of the substrate before immersion was calculated according to JIS Z 8729.
The rank of evaluation is as follows. In the evaluation results, ◯ is good, Δ is a level that does not cause a problem in use, and × corresponds to a state where it cannot be used.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
○: ΔEab * is less than 3 Δ: ΔEab * is 3 or more and less than 8 ×: ΔEab * is 8 or more

<Sensitivity evaluation>
The pattern film thickness in the 100 μm photomask portion of the filter segment formed by the above method was measured, and the minimum exposure amount that was 90% or more with respect to the film thickness after coating was evaluated. It can be said that the smaller the minimum exposure, the higher the sensitivity and the better the photosensitive coloring composition.
The rank of evaluation is as follows. In the evaluation results, ◯ is good, Δ is a level that does not cause a problem in use, and × corresponds to a state where it cannot be used.
○: Less than 50 mJ / cm ² Δ: 50 mJ / cm ² or more and less than 100 mJ / cm ² ×: 100 mJ / cm ² or more

  A colored composition containing a xanthene dye and not containing an antioxidant [C] or a melamine compound [D] is reduced in brightness by heat treatment at 230 ° C. in the color filter forming step, and is a pigment-based colored composition only. It has become the same level as lightness.

  On the other hand, the coloring composition for a color filter of the present invention containing the antioxidant [C] or the melamine compound [D] has high brightness after heat treatment at 230 ° C., and excellent performance in heat resistance and solvent resistance. Demonstrated.

  Among the antioxidants [C], the coloring composition containing a phenol-based antioxidant and a sulfur-based antioxidant or a phosphorus-based antioxidant has high brightness and excellent sensitivity.

  The coloring composition for a color filter of the present invention containing a melamine compound [D] has a very high brightness after heat treatment at 230 ° C. and excellent performance as compared with a coloring composition containing another crosslinking agent (epoxy resin). did.

Claims (9)

  A coloring composition for a color filter comprising a coloring agent [A] containing a xanthene dye [A1], a binder resin [B], and an antioxidant [C].   The coloring composition for a color filter according to claim 1, wherein the xanthene dye [A1] is a salt forming compound of a xanthene acid dye and / or a sulfonic acid amide compound of a xanthene acid dye.   The antioxidant [C] is at least one kind of antioxidant selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants. Or the coloring composition for color filters of 2.   The content of the antioxidant [C] is 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition. The coloring composition for color filters as described in above.   A color composition for a color filter comprising a colorant [A] containing a xanthene dye [A1], a binder resin [B], and a melamine compound [D].   6. The coloring composition for a color filter according to claim 5, wherein the xanthene dye [A1] is a salt forming compound of a xanthene acid dye and / or a sulfonic acid amide compound of a xanthene acid dye.   The colored composition for a color filter according to claim 5 or 6, wherein the content of the melamine compound [D] is 2 to 30 parts by weight with respect to 100 parts by weight of the colorant [A].   Furthermore, polyfunctional monomer [E] and / or photoinitiator [F] are contained, The coloring composition for color filters of any one of Claims 1-7 characterized by the above-mentioned.   A color filter comprising a filter segment formed from the colored composition for a color filter according to claim 1 on a substrate.