JP6972580B2 - Coloring compositions and color filters for color filters - Google Patents

Description

The present invention relates to a coloring composition for a color filter used in manufacturing a color filter used for manufacturing a color liquid crystal display device, a color image pickup element, and the like, and a color filter including a filter segment formed by using the coloring composition. be.

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

For color filters, a grid-like light-shielding film black matrix (hereinafter referred to as BM) is provided on a transparent substrate such as a glass plate to prevent color mixing of transmitted light and enhance display contrast, and then multiple colors (usually red, usually red) are provided for each pixel. Green, blue) filter segments are provided. The filter segments are as fine as several microns to several hundreds of microns, and the arrangement of the filter segments is arranged in a fine band (stripes) of two or more different hues (striped arrangement), or an arrangement of constant length and width. There are those arranged in (delta arrangement) and the like. The filter segment and BM are formed by applying a coloring composition and drying at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

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 orienting the liquid crystal in a certain direction is further formed on the transparent electrode. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher. Therefore, as a method for manufacturing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is currently the mainstream.

In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitizer, an additive, etc. with a resin in which pigment particles, which are colorants, are dispersed, and this color resist is applied onto a substrate by a coating device such as a spin coater. This is a method of forming a coating film, selectively exposing it through a mask with an aligner, a stepper, or the like, patterning it by performing alkaline development and heat curing treatment, and repeating this operation to produce a color filter.

Brightness and contrast ratio are examples of quality items required for color filters. If a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light leaks or when light must be transmitted (ON). Since the transmitted light is attenuated in the state), the screen becomes blurry. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

Further, if a color filter having a low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. Therefore, from the viewpoint of suppressing the increase in power consumption, the trend is to increase the brightness of color filters. Further, as described above, since color liquid crystal displays have come to be used for televisions, personal computer monitors, and the like, there is an increasing demand for high reliability as well as high brightness and high contrast for color filters.

In order to achieve high brightness and high contrast, mainly diketopyrrolopyrrole pigments and anthraquinone pigments are used alone or in combination in the red filter segments of the three primary colors (red, green, blue; RGB) of the color filter substrate. In general, a phthalocyanine pigment and a quinophthalone pigment are used alone or in combination for the green filter segment.

However, although the diketopyrrolopyrrole pigment and the quinophthalone pigment are excellent in brightness, there is a problem in heat resistance when they are used in a finely divided form. In recent years, there has been a strong demand for high contrast in color filters, and for that purpose, it is necessary to make the primary particle size of diketopyrrolopyrrole pigments and quinophthalone pigments as fine as possible. However, there is a problem that the finely divided diketopyrrolopyrrole pigments and quinophthalone pigments crystallize and precipitate in the heating step when forming the color filter.

As a study for improving crystal precipitation, Patent Document 1 and Patent Document 2 disclose a coloring composition for a color filter in which crystal precipitation is suppressed by connecting a quinophthalone skeleton with a resin to form a dye multimer. Further, Patent Document 3 discloses a coloring composition for a color filter in which a substituent is added to a quinophthalone skeleton to suppress crystal precipitation in order to improve the heat resistance of the quinophthalone pigment. In Patent Documents 4 and 5, a diketopyrrolopyrrole pigment (mainly CI Pigment Red 254), a diaryldiketopyrrolopyrrole compound having at least one specific structural formula, and a pigment derivative are combined. A coloring composition for a color filter, which has high contrast and suppresses crystal precipitation due to a heating step by use, is disclosed. However, although these methods have improved the crystal precipitation to some extent, they have not been completely suppressed, and there are also problems such as pigment multimers, changes in the skeleton, deterioration of brightness due to the addition of derivatives, and deterioration of developability. Has also occurred, and further improvement is desired.

JP-A-2016-105169 (Fujifilm resin-linked quinophthalone synthesis) JP-A-2016-035068 (Fujifilm resin-linked quinophthalone synthesis) JP-A-2016-145282 (Toyo Ink Kinophthalone Skeleton Synthesis) International Publication No. 2009/081930 Pamphlet Japanese Unexamined Patent Publication No. 2009-149707

An object of the present invention is a coloring composition for a color filter in which crystal precipitation is suppressed even in a heat treatment of 270 ° C. or higher in a color filter manufacturing process, and a high-brightness color formed by using the coloring composition for a color filter. To provide a filter.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have significantly improved heat resistance and crystal precipitation of a coloring composition for a color filter containing a resin having a specific structure, and have high brightness. We have found that a color filter can be obtained.

[一般式（１）中、Ｒ₁、Ｒ₂、Ｒ₃は、それぞれ互いに独立して、−Ｈまたは−ＣＨ₃であり、Ｒ₄は

のいずれかであり、Ｒ_５は
−（ＣＨ_２）_n−、−Ｃ_６Ｈ₄−、−Ｃ_６Ｈ₁₀−、−Ｃ_２Ｈ_２−、
のいずれかであり、ｍ、ｎは、１〜４の整数である。］ That is, the present invention is a coloring composition containing a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D) and a thiol compound (E). The resin (B) has a structural unit represented by the following general formula (1), and the acid value derived from the structural unit represented by the following general formula (1) is 100 to 170 mgKOH / g. The present invention relates to a coloring composition for a color filter, wherein the coloring agent (A) contains a coloring agent having a quinophthalone skeleton (A1) or a coloring agent having a diketopyrrolopyrrole skeleton (A2).

General formula (1)

[In the general formula (1), R ₁ , R ₂ , and R ₃ are each independently of −H or −CH ₃ , and R ₄ is.

R ₅ is − (CH ₂ ) _n −, −C ₆ H ₄ −, −C ₆ H ₁₀ −, −C ₂ H ₂ −,
, And m and n are integers of 1 to 4. ]

The present invention also relates to the coloring composition for a color filter, wherein the coloring agent (A) contains a coloring agent (A1) having a quinophthalone skeleton.

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

Further, the present invention relates to a liquid crystal display device provided with the color filter.

With the coloring composition for a color filter of the present invention, even when a heat treatment of 230 ° C. or higher is performed in the manufacturing process of a color filter, a high-brightness filter segment can be formed without crystal precipitation.

Hereinafter, embodiments of the present invention will be described in detail.
In the present application, when "(meth) acrylate", "(meth) acrylic acid", or "(meth) acrylamide" is described, "acrylate and / or methacrylate", respectively, unless otherwise specified. It shall represent "acrylic acid and / or methacrylic acid" or "acrylamide and / or methacrylamide".
Further, "CI" mentioned in the present specification means a color index (CI).

The coloring composition for a color filter of the present invention is characterized by containing a coloring agent, a resin, a photopolymerization monomer, and an organic solvent.
First, various constituents of the coloring composition for a color filter of the present invention will be described.

［一般式（４）中、Ｘ１〜Ｘ１３は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有しても良いアルキル基、置換基を有しても良いアルコキシル基、置換基を有しても良いアリール基、−ＳＯ_３Ｈ基、−ＣＯＯＨ基、−ＳＯ_３Ｈ基もしくは−ＣＯＯＨ基の金属塩、−ＳＯ_３Ｈ基もしくは−ＣＯＯＨ基のアルキルアンモニウム塩、置換基を有しても良いフタルイミドメチル基、または置換基を有しても良いスルファモイル基を示す。ただし、Ｘ１〜Ｘ４、および／または、Ｘ１０〜Ｘ１３の隣接した基は、一体となって、置換基を有してもよい芳香環を形成する。］ <Coloring composition for color filters>
<< Colorant (A) >>
The colorant (A) of the present invention contains a quinophthalone pigment which is a colorant (A1) having a quinophthalone skeleton or a diketopyrrolopyrrole pigment which is a colorant (A2) having a diketopyrrolopyrrole skeleton. The coloring compositions of the invention can be used primarily to make pixels for green or yellow or red color filters.

<Kinophthalone pigment (A1)>
The quinophthalone-based pigment of the present invention is a known pigment, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 231 can be mentioned. The quinophthalone pigment also includes the following general formula (4). The content of the quinophthalone pigment is preferably 10 to 70 parts by weight, preferably 100 parts by weight of the colorant.
General formula (4)

[In the general formula (4), X1 to X13 each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. It is aryl group, -SO ₃ H group, -COOH group, a metal salt of -SO ₃ H group or a -COOH group, an alkyl ammonium salt of the -SO ₃ H group or a -COOH group, which may have a substituent Indicates a good phthalimidemethyl group, or a sulfamoyl group which may have a substituent. However, adjacent groups of X1 to X4 and / or X10 to X13 together form an aromatic ring that may have a substituent. ]

Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a petit group, an isoptyl group, a tert-ptyl group, a neopentyl group, an n-hexyl group and an n-octyl group. In addition to a linear or branched alkyl group such as a group, a stearyl group and a 2-ethylhexyl group, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group and a 2,2-dibromoethyl group, 2,2,3,3-Tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, pendyl group, 4-methylpentyl group, 4-tert-ptylbenzyl group, 4-methoxy Examples thereof include an alkyl group having a substituent such as a penzyl group, a 4-nitrobenzyl group and a 2,4-dichlorobenzyl group.

Examples of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isoptyloxy group, a tert-ptyloxy group, a neopentyloxy group, 2, In addition to linear or branched alkoxyl groups such as 3-dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group and 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro Examples thereof include an alkoxyl group having a substituent such as a propoxy group and a benzyloxy group.

The aryl group which may have a substituent includes an aryl group such as a phenyl group, a naphthyl group and an anthranyl group, as well as a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group and a p-. Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-Trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and other aryl groups having substituents can be mentioned.

As the acidic _group, -SO 3 H, -COOH, and examples of the monovalent to trivalent metal salt thereof acidic groups, sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts And so on. Examples of the alkylammonium salt of the acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, and quaternary alkyls such as palmityltrimethylammonium, dilauryldimethylammonium and distealyldimethylammonium salts. Ammonium salt can be mentioned.

A "substituent" in a phthalimidemethyl group (C ₆ H ₄ (CO) ₂ N-CH _2- ) which may have a substituent and a sulfamoyl group (H ₂ NSO _2- ) which may have a substituent. Examples thereof include the above-mentioned halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent and the like.

Adjacent groups of X1 to X4 and / or X10 to X13 of the general formula (4) together form an aromatic ring which may have a substituent. Examples of the aromatic ring here include a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, and the heteroaromatic ring includes pyridine. Examples thereof include a ring, a pyrazine ring, a pyrrol ring, a quinoline ring, a quinoxalin ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring.

(Diketopyrrolopyrrole pigment)
The diketopyrrolopyrrole pigment of the present invention is a known pigment, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 272, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73. When the coloring composition of the present invention is used for a color filter application, C.I. I. It is most preferable to use Pigment Red 254 in terms of having high brightness. The content of the diketopyrrolopyrrole pigment is preferably 60 to 90 in an amount of 100 parts by weight of the colorant.
(Other colorants)
Further, as another colorant that can be used in the coloring composition of the present invention, various conventionally known pigments and dyes can be arbitrarily selected. These pigments / dyes can be used alone or in admixture of two or more at any ratio as required.
As the pigment, conventionally known organic pigments and inorganic pigments can be used.

(Organic pigment)
Examples of the organic pigment include azo pigments such as azo, disazo, or polyazo, anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, antoanthron, indantron, pyranthron, or biolantron, and quinacridone pigments. Examples thereof include perinone pigments, perylene pigments, thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, slene pigments and metal complex pigments.

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, 58, 62 or 63. Can be done. Among these, from the viewpoint of lightness and coloring power, C.I. I. Pigment Green 7, 36, 58, 62 or 63. Further, the zinc phthalocyanine pigments and the like described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-070342 and the like can also be used, and the present invention is not particularly limited thereto.

Specifically, as these organic pigments,
As a red pigment, for example, 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, 179, 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, 256 , 257, 258, 259, 260, 262, 263, 265, 266, 267, 268, 269, 270, 271, 273, 274, 275, 276 and the like.
Examples of the orange pigment that works in the same manner as the red pigment include C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61 and other orange pigments can be used.
Among these, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. I. Pigment Red 177, C.I. I. It is particularly preferred to use Pigment Red 269.

In the coloring composition of the present invention, a yellow pigment can be used as a green and yellow and red toning pigment.
Examples of the yellow pigment 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, 173, 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 can be mentioned. 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 the purple pigment 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 can be mentioned. 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.

The content of the colorant is preferably 10% by weight or more, more preferably 15% by weight or more, most preferably 15% by weight or more, based on the total non-volatile components of the coloring composition as a reference (100% by weight) from the viewpoint of obtaining sufficient color reproducibility. It is preferably 20% by weight or more. Further, from the viewpoint of the stability of the coloring composition, the preferable colorant content is 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less.

(dye)
Next, a dye that can be used in combination with the quinophthalone-based pigment and the diketopyrrolopyrrole-based pigment in the coloring composition of the present invention will be described. Examples of dyes that can be used in combination include compounds classified as dyes in the Color Index (published by The Society of Dyers and Colorists) and known dyes described in Dyeing Note (Dyeing Co., Ltd.). , Oil-soluble dyes, acidic dyes, metal complex salt dyes, basic dyes, direct dyes, disperse dyes, medium dyes and the like. Of these, oil-soluble dyes, acid dyes, metal complex salt dyes, and basic dyes are preferable.
According to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridin dye, styryl dye, coumarin dye, quinoline. Examples include dyes and nitro dyes.

<Oil-soluble dye>
When an oil-soluble dye is used, a xanthene dye or an anthraquinone dye is preferable from the viewpoint of lightness.
Examples of xanthene-based 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, CI Solvent Red 46, CI Solvent Red 47, CI Solvent Red 48, CI Solvent Red 49, CI Solvent Red 72, CI. 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, or C.I.
I. Solvent Violet 10 and the like.

Among them, CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 49, CI Solvent Red 109, and CI Solvent Red, which are rhodamine-based oil-soluble dyes with high color development. Red 237, CI Solvent Red 246 and CI Solvent Violet 2 are more preferred.

As anthraquinone-based oil-soluble dyes, CI Solvent Red 172, 222, C.I.
I. Solvent Violet 60 and the like.

<Acid dye>
As triarylmethane acid dyes, CI Acid Blue 1, 3, 5, 7, 9
, 11, 15, 17, 19, 22, 24, 38, 48, 75, 83, 90, 91, 93, 93: 1,100, 103, 104, 109, 110, 119, 147, 269, 123, 213. , CI Direct Blue 41, CI Acid Violet 17, 19, 21, 23, 25, 38, 49, 72, Direct Blue 41 and the like.

Examples of the xanthene-based acid dye include C.I. I. Acid Red 51 (erythrosine (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 Phloxine 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 them, C.I., a xanthene-based acid dye, is a xanthene-based acid dye in terms of heat resistance and light resistance. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or Rhodamine-based 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, C.I., which is a rhodamine-based acid dye, is particularly excellent in color development, heat resistance, and light resistance. I. Acid Red 52, C.I. I. It is most preferable to use Acid Red 289.

Anthraquinone acid dyes include CI Acid Blue 23, 25, 27, 35.
, 40, 41, 43, 45, 47, 49, 51, 53, 55, 56, 62, 68, 69, 78, 80, 81: 1, 11, 124, 127, 127: 1, 140, 150, 175 , 215, 230, 277, 344, CI Acid Violet 41, 42, 43, CI Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105 , 106, 109, or Direct Violet 17 and the like.

Examples of the azo acid dye include CI Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108. , 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337;
CI Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127;
CI Acid Violet 11, 56, 58;
CI Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151;
CI Acid Brown 2, 4, 13, 248;
CI Acid Blue 92, 102, 113, 117 and the like can be mentioned.

[Salt-forming compounds of acid dyes]
As the dye used in combination with the quinophthalone-based pigment and the diketopyrrolopyrrole-based pigment in the present invention, an acidic dye is preferable from the viewpoint of heat resistance and light resistance, and a salt-forming compound of the acidic dye and a nitrogen-containing compound from the viewpoint of stability. Is more preferable, and chloride is formed using a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, and a resin component having these functional groups to produce a xanthene-based acidic dye. The salt compound is particularly preferable because it can impart high heat resistance, light resistance, and solvent resistance.
Further, it may be a salt-forming compound of an acid dye and a compound having an onium base, and among them, the compound having an onium base is a resin having a cationic group in the side chain, so that the lightness and resistance can be improved. It can be an excellent coloring composition.

"Resin having a cationic group in the side chain"
A resin having a cationic group in the side chain will be described. The resin having a cationic group in the side chain for obtaining the salt-forming compound is not particularly limited as long as it has at least one onium base in the side chain, but is available as a suitable onium salt structure. From the viewpoint of the above, ammonium salt, iodonium salt, sulfonium salt, diazonium salt, and phosphonium salt are preferable, and in consideration of storage stability (thermal stability), ammonium salt, iodonium salt, and sulfonium salt are used. Is more preferable. More preferably, it is an ammonium salt.

The resin having a cationic group in the side chain is an alkaline resin containing a structural unit represented by the following general formula (5), and the cationic group in the general formula (5) is an anionic group of a xanthene acid dye. By forming a salt, a salt-forming compound can be obtained.

［一般式（５）中、Ｒ^５１は水素原子、または置換もしくは無置換のアルキル基を表す。Ｒ^５２〜Ｒ^５４は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、または置換されていてもよいアリール基を表し、Ｒ^５２〜Ｒ^５４のうち２つが互いに結合して環を形成しても良い。Ｑはアルキレン基、アリーレン基、−ＣＯＮＨ−Ｒ^５５−、−ＣＯＯ−Ｒ^５５−を表し、Ｒ^５５はアルキレン基を表す。Ｙ⁻は無機または有機のアニオンを表す。］ General formula (5)

[In the general formula (5), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ^{52 to} R ⁵⁴ independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, respectively, of R ^{52 to} R ⁵⁴ . Two of them may be combined with each other to form a ring. Q represents an alkylene group, an arylene ^{group, -CONH-R 55 -, -} COO-R 55 - ^{represents, R 55} represents an alkylene group. Y ⁻ represents an inorganic or organic anion. ]

"Salt formation with acid dyes"
The salt-forming compound of the acid dye and the resin having a cationic group in the side chain can be produced by a conventionally known method. A specific method is disclosed in JP-A-11-72969.
To give an example using a xanthene-based acid dye, a quaternary ammonium salt compound may be added after dissolving the xanthene-based acid dye in water, and the chloride-forming treatment may be performed while stirring. Here, the sulfonic acid group (-SO ₃ H) and sodium sulfonate group (-SO ₃ Na) in the xanthene-based acidic dye and the ammonium group (NH ₄ ⁺ ) in the quaternary ammonium salt compound are bonded. A salt compound is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used during chloride formation.

Further, the salt-forming compound used in the present invention is prepared by stirring or vibrating an aqueous solution prepared by dissolving a resin having a cationic group in a side chain represented by the general formula (5) and an acid dye, or using the general formula (5). ), An aqueous solution of a resin having a cationic group in the side chain and an aqueous solution of an acid dye are mixed with stirring or vibration to easily obtain the solution. In the aqueous solution, the ammonium group of the resin and the anionic group of the acid dye are ionized, and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, since the salt composed of the counter anion of the resin and the counter cation of the acid dye is water-soluble, it can be removed by washing with water or the like. As the resin having a cationic group in the side chain and the acid dye, only one kind may be used, or a plurality of kinds having different structures may be used.

<Metal complex salt dye>
The metal complex salt dye can be suitably used because it exhibits a fluorescence quenching effect on a dye having fluorescence.
Examples of the metal complex salt dye include C.I. I. Solvent Yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161. I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99, C.I. I. Solvent Red 8, 35, 83: 1, 84: 1, 90, 90: 1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243; C.I. I. Solvent Violet 2, 21, 21: 1, 46, 49, 58, 61; C.I. I. Solvent Blue 137; C.I. I. Solvent Brown 28, 42, 43, 44, 53, 62, 63; C.I. I. Acid Yellow 59, 121; C.I. I. Acid Orange 74, 162; C.I. I. Acid Red 211 is mentioned. Among these, from the viewpoint of fluorescence quenching, C.I. I. Solvent Yellow 21, 79, 81, 82, C.I. I. Solvent Orange 41, 54, 56, 62, 99, C.I. I. Solvent red 8, 118, 122, 127 are preferred. These metal complex salt dyes may be used alone or in combination of two or more.

When the colorant contains a dye, the content of the dye is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the pigment. More preferably, it is 20 to 30 parts by weight. When the amount of the dye added is within this range, the brightness, the contrast ratio, the heat resistance, and the chemical resistance can be made excellent. In the coloring composition for a color filter of the present invention, it is preferable that the coloring agent contains both a pigment and a dye from the above viewpoint.

<Pigment miniaturization>
When a pigment is used in the present invention, it is preferable to use it in a finely divided manner, but the finening method is not particularly limited, and for example, wet grinding, dry grinding, and dissolution precipitation method can be used and are exemplified in the present invention. Therefore, the salt milling treatment by the kneader method, which is a kind of wet grinding, can be performed. The primary particle size of the pigment is preferably 20 nm or more because it is well dispersed in the colorant carrier. Further, since a color filter having a high contrast ratio can be formed, it is preferably 100 nm or less. A particularly preferable range is the range of 25 to 85 nm. The primary particle size of the pigment was determined by a method of directly measuring the size of the primary particle from an electron micrograph of the pigment by a TEM (transmission electron microscope). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle size of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to a cube having a obtained particle size, and the volume average particle size is defined as the average primary particle size.
The coloring composition of the present invention contains an epoxy compound together with a specific pigment dispersant containing a heat-crosslinkable functional group, and thus has excellent resistance even when such a finely divided pigment is used. , A coloring composition for a color filter having a high luminance and contrast ratio.

Salt milling is a machine that heats a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, and a 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 acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

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 price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, most preferably 300 to 1000 parts by weight, based on 100 parts by weight of the pigment.

The water-soluble organic solvent has a function of wetting 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 used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. 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, most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

When the pigment is subjected to salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, 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.

<Pigment dispersant>
When the colorant (A) is dispersed in the colorant carrier, a dispersion aid such as a dye derivative, a resin-type dispersant, or a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersing the colorant and has a great effect of preventing the reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in the pigment carrier using the dispersion aid is used. If so, a color filter with high spectral transmittance can be obtained.

Examples of the dye derivative include a compound in which an organic pigment, anthraquinone, acrydone or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimidemethyl group which may have a substituent.
Of these, pigment derivatives are preferable, and their structures are compounds represented by the following general formula (4).
P-Ln general formula (4)
(However,
P: Organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: Basic substituent, acidic substituent, or phthalimide methyl group n: an integer of 1 to 4 which may have a substituent. be)
Examples of the organic pigment constituting the organic pigment residue of P include diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine. Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, antoanthron, indantron, pyranthron, biolantron; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; iso Examples thereof include indolin-based pigments; isoindolinone-based pigments; quinophthalone-based pigments; slene-based pigments; and metal complex-based pigments.

Examples of the dye derivative are described in JP-A-63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-1469, and the like. These can be used alone or in admixture of two or more.
The blending amount of the dye derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, and most preferably 3% by weight or more with respect to 100 parts by weight of the colorant (A) from the viewpoint of improving dispersibility. be. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40% by weight or less, and most preferably 35% by weight or less, based on 100 parts by weight of the colorant (A).

The resin-type dispersant has a pigment-affinitive moiety having a property of adsorbing to the colorant and a moiety compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant on the colorant carrier. It works to stabilize. Specific examples of the resin-type dispersant 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 polyaminoamidophosphate, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Oil-based dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and the like water-soluble Resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphoric acid ester-based, etc. are used, and these can be used alone or in admixture of two or more. It is not necessarily limited to these.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, manufactured by Japan Lubrizol. 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, 452 manufactured by BASF. 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540 , 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Can be mentioned.

Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalline sulfonate, sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Polyoxyethylene alkyl ether phosphate and other anionic surfactants; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolin, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

When the resin type dispersant and the surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, based on 100 parts by weight of the colorant (A). When the blending amount of the resin type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the effect of addition, and when the blending amount is more than 55 parts by weight, the dispersion is affected by the excess dispersant. May affect.

[一般式（１）中、Ｒ₁、Ｒ₂、Ｒ₃は、それぞれ互いに独立して、−Ｈまたは−ＣＨ₃であり、Ｒ₄は

のいずれかであり、Ｒ_５は
−（ＣＨ_２）_n−、−Ｃ_６Ｈ₄−、−Ｃ_６Ｈ₁₀−、−Ｃ_２Ｈ_２−、
のいずれかであり、ｍ、ｎは、１〜４の整数である。 << Resin (B) >>
The coloring composition of the present invention has a constituent unit represented by the following general formula (1), and has a resin B having an acid value of 100 to 170 mgKOH / g according to the constituent unit represented by the following general formula (1). ..
In addition, (meth) acrylic acid represents acrylic acid or methacrylic acid, and (meth) acrylate represents acrylate or methacrylate.
General formula (1)

[In the general formula (1), R ₁ , R ₂ , and R ₃ are each independently of −H or −CH ₃ , and R ₄ is.

R ₅ is − (CH ₂ ) _n −, −C ₆ H ₄ −, −C ₆ H ₁₀ −, −C ₂ H ₂ −,
, And m and n are integers of 1 to 4.

Since the acid group of the structural unit represented by the general formula (1) in the resin (B) used in the coloring composition of the present invention exists at a distance from the main chain, it is difficult to be fixed by the main chain and is free. The degree is high. Therefore, the quinophthalone-based pigment or the diketopyrrolopyrrole-based pigment interacts with the acid group to suppress pigment aggregation due to heating, so that a highly heat-resistant coloring composition without crystal precipitation can be obtained.

The structural unit represented by the general formula (1) is particularly the structural unit formed from the succinic anhydride modified product represented by the formula (6) and the phthal represented by the formula (7). A structural unit formed from an acid monohydroxyethyl acrylate, a structural unit formed from an acrylic acid dimer represented by the formula (8) is preferable, and among them, it is formed from a succinic anhydride modified product of 2-hydroxyethyl methacrylate. Constituent units are particularly preferred.

Equation (6)

Equation (7)

Equation (8)

Further, in the resin B, the acid value derived from the structural unit represented by the general formula (1) is preferably 100 to 170 mgKOH / g, and the acid value derived from the structural unit represented by the general formula (1) is preferably 100 to 170 mgKOH / g. More preferably, it is 120 to 150 mgKOH / g. If the acid value according to the structural unit represented by the general formula (1) is less than 100 mgKOH / g, crystals of a quinophthalone-based pigment or a diketopyrrolopyrrole-based pigment are precipitated due to deterioration of heat resistance, and if it is 170 mgKOH / g or more. A highly dispersible coloring composition cannot be obtained.

As the other structural unit represented by the general formula (1), known polybasic acid anhydrides can be used as the polybasic acid anhydride added to the hydroxyl group of the copolymer. For example, maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride can be mentioned.

The acid value of the resin derived from the structural unit represented by the general formula (1) was calculated according to the following formula.

Resin acid value (mgKOH / g) derived from the structural unit represented by the general formula (1).
= {F ₁ / m ₁ + f ₂ / m ₂ + ...)} × 56100

f: Weight (g) of acid value of the carboxyl group-containing unsaturated monomer of the structural unit represented by the general formula (1).
m: Molecular weight (g / mol) of the acid value of the carboxyl group-containing unsaturated monomer of the structural unit represented by the general formula (1).

The resin B of the coloring composition of the present invention may have a structural unit derived from other monomers in addition to the structural unit represented by the general formula (1). Examples of other monomers include alkyl ester (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl methacrylate, stearyl methacrylate, and cyclohexyl methacrylate. Kind, styrene, α-methylstyrene, vinyltoluene, vinyl acetate, vinylacrylic acid propionate, acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, monohydroxyethyl phthalate, maleic acid, itaconic acid, fumaric acid, Glutaconic acid, tetrahydrophthalic acid, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) Acrylate, 2-hydroxybutyl (meth) acrylate, glycerin (meth) acrylate, polycaprolactone-modified hydroxyethyl (meth) acrylate (number of repetitions of caprolactone = 1 to 6), epoxy (meth) acrylate, hydroxyl group-terminated urethane (meth) acrylate Examples thereof include, but are not limited to, ethylenically unsaturated monomers. Further, one kind or two or more kinds of these can be used.

<< Photopolymerizable Monomer (C) >>
The photopolymerizable monomer (C) is cured by ultraviolet rays, heat, or the like to form a transparent resin, and can be used alone or in combination of two or more. The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight based on the total weight of the colorant (B) (100 parts by weight), and is 10 to 10 by weight from the viewpoint of photocurability and developability. More preferably, it is 300 parts by weight.
Examples of the photopolymerizable monomer (C) used in the coloring composition for a color filter of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth). ) Acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neo Pentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane. Various acrylic acid esters such as acrylates and methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide. , N-vinylformamide, acrylonitrile and the like, but are not necessarily limited thereto.

<< Photopolymerization Initiator (D) >>
When the composition is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator or the like is added to the coloring composition for a color filter of the present invention. The photopolymerization initiator can be used in an amount of preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight, based on the total weight of the colorant (A) (100 parts by weight).
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1-. Hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetphenone-based photopolymerization initiators such as -1-one, benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, Benzophenone-based photopolymerization initiators such as 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, thioxanson, 2-chlorthioxanson, 2-methylthioxanson, isopropylthioxanson. , 2,4-Diisopropylthioxanson and other thioxanson-based photopolymerization initiators, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (P-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6 -Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4- Triazine-based photopolymerization initiators such as trichloromethyl (4'-methoxystyryl) -6-triazine, borate-based photopolymerization initiators, carbazole-based photopolymerization initiators, imidazole-based photopolymerization initiators and the like are used.

These photopolymerization initiators are used alone or in admixture of two or more, but as sensitizers, α-acyloxyester, acylphosphine oxide, methylphenylglycilate, benzyl-9,10-phenone Renquinone, phenylquinone, ethylanthraquinone, 4,4'-diethylisophthalofenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone, etc. Compounds can also be used in combination. The sensitizer can be used in an amount of 0.1 to 60 parts by weight, preferably 0.1 to 60 parts by weight, based on 100 parts by weight of the photopolymerization initiator.

<< Thiol compound (E) >>
The coloring composition for a color filter of the present invention is characterized by containing a thiol compound (E). When the thiol compound (E) is used together with the above-mentioned photopolymerization initiator, it acts as a chain transfer agent in the radical polymerization process after light irradiation and generates a chile radical that is not easily inhibited by oxygen, so that a color filter can be obtained. The coloring composition for use is highly cross-linked. Therefore, the pigment in the coloring composition is captured, and at the same time, the momentum of the pigment is reduced, so that the interaction with the acid group of the structural unit represented by the general formula (1) is likely to occur, and the aggregation due to heating is suppressed, so that the heat resistance is reduced. Improvement is seen. In particular, a polyfunctional aliphatic thiol compound in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

Examples of the thiol compound (E) include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthio. Propionate, Trimethylolpropane Tristhioglycolate, Trimethylolpropane Tristhiopropionate, Trimethylolethanetris (3-mercaptobutyrate), Trimethylolpropanetris (3-mercaptobutyrate), Trimethylolpropanetris (3-mercaptobutyrate) 3-Mercaptopropionate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetrakissthiopropionate, Pentaerythritol Tetrakiss (3-Mercaptopropionate), Dipentaerythritol Hexakis (3-Mercaptopropionate), Tri Tris (2-hydroxyethyl) mercaptopropionate isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto -S-Triazine and the like can be mentioned.
These thiol compounds (E) can be used alone or in admixture of two or more at any ratio as required.

The content of the thiol compound (E) is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5.0 parts by weight, based on 100 parts by weight of the resin (B).
By using 0.05 parts by weight or more of the thiol compound (E), the cross-linking points of the coloring composition are increased, and a coloring composition having higher heat resistance and suppressing crystal precipitation can be obtained.

"Organic solvent"
Further, as the organic solvent, the colorant is sufficiently dispersed in the transparent resin, and the coloring composition of the present invention is applied onto a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to obtain a filter. It is used to facilitate the formation of segments. The organic solvent can be used in an amount of preferably 800 to 4000 parts by weight, more preferably 1000 to 2500 parts by weight, based on the total weight of the colorant (A) (100 parts by weight).
Organic solvents include 1,2,3-trichloropropane, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol. 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3- Methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide , N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate, 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 monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether , Diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, di Diethyl Glycol Monoethyl Ether, Dipropylene Glycol 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 ketone, methyl cyclohexanol, acetic acid n- Examples thereof include amyl, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like, and these can be used alone or in combination.

<< Other additives >>
A dispersion aid such as a surfactant can be appropriately used in the coloring composition for a color filter of the present invention. Since the dispersion aid is excellent in dispersing the colorant and has a great effect of preventing the reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in a transparent resin using the dispersion aid was used. In some cases, a color filter with excellent transparency can be obtained. The dispersion aid can be used in an amount of preferably 0.1 to 60 parts by weight, more preferably 0.1 to 45 parts by weight, based on the total weight of the colorant (A) (100 parts by weight).
Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalline sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, and lauryl. Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples thereof include alkyl betaines such as alkyl dimethylamino acetate betaine and amphoteric surfactants such as alkyl imidazoline, which can be used alone or in admixture of two or more.

The coloring composition for a color filter of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on the total weight of the colorant (A) (100 parts by weight).
Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphoric acid and their methyl ethers, and organic acids such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples include phosphine and phosphite.

<< Manufacturing method of coloring composition for color filter >>
In the coloring composition for a color filter of the present invention, a colorant is placed in a colorant carrier such as a resin and / or a solvent together with a dispersant aid, if necessary, in a kneader, a 2-roll mill, a 3-roll mill, and a ball mill. , Horizontal sand mill, vertical sand mill, annular bead mill, or attritor can be used to finely disperse and produce (colorant dispersion). At this time, two or more kinds of colorants and the like may be dispersed in the colorant carrier at the same time, or those dispersed separately in the colorant carrier may be mixed.
If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, it is manufactured by finely dispersing it as described above. No need.

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent-developing type or alkali-developing type coloring composition. The solvent-developed or alkaline-developed coloring composition is a mixture of the colorant dispersion, a polyfunctional monomer and / or a photopolymerization initiator, and if necessary, a solvent, other pigment dispersants, additives and the like. Can be adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises a filter segment formed by using the coloring composition for a color filter of the present invention. Color filters include those comprising a red filter segment, a green filter segment, and a blue filter segment, or those comprising a magenta color filter segment, a cyan filter segment, and a yellow color filter segment.

As the transparent substrate, a glass plate such as soda-lime glass, low-alkali borosilicate glass, or non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used. Further, a transparent electrode made of indium oxide, tin oxide or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal display after the panelization.

<< Manufacturing method of color filter >>
The color filter of the present invention can be manufactured by a printing method or a photolithography method.

The formation of filter segments by the printing method can be patterned simply by repeating printing and drying of the coloring composition prepared as printing ink, so that it is low cost and excellent in mass productivity as a manufacturing method of color filters. There is. Furthermore, with the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted by using a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent-developable or alkali-developable colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, and the coloring composition of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on the transparent substrate or the reflective substrate. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but the black matrix is not limited thereto. Further, it is also possible to form a thin film transistor (TFT) in advance on the transparent substrate or the reflective substrate, and then form each color filter segment. Further, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention, if necessary.

The color filter is bonded to the facing substrate using a sealing agent, the liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is placed on the outside of the substrate as necessary. By laminating, a liquid crystal display panel is manufactured.

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

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" mean "parts by weight" and "% by weight".

The method for measuring the weight average molecular weight (Mw) of the resin and the method for calculating the acid value (mgKOH / g) of the resin are as follows.

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

<< Acid value of resin (mgKOH / g) >>
The acid value of the resin was calculated according to the following formula.

Resin acid value (mgKOH / g) = {f ₁ / m ₁ + f ₂ / m ₂ + ...)} × 56100

f: Weight of acid value of unsaturated monomer containing carboxyl group (g)
m: Molecular weight of acid value of unsaturated monomer containing carboxyl group (g / mol)

Subsequently, a method for producing an acrylic resin solution used in Examples and Comparative Examples, a method for producing a micronized pigment, a method for preparing a pigment dispersant solution, a method for producing a pigment dispersion, a method for producing a salt-forming compound of a dye, and the like. A method for producing a dye-containing solution will be described.

<< Manufacturing method of acrylic resin solution >>
(Synthesis of polymerizable monomer (monomer A))
Monomer A was obtained by reacting the hydroxyl group of 2-hydroxyethyl methacrylate with succinic anhydride.
(Acrylic resin solution (B-1))
194.0 parts of propylene glycol monoethyl ether acetate was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, heated to 80 ° C., and the inside of the reaction vessel was filled with nitrogen. After substitution, 180.0 parts of Monomer A, 15.0 parts of 2-hydroxyethyl methacrylate, 15.0 parts of tert-butyl methacrylate, 30.0 parts of benzyl methacrylate, and 15. of n-butyl methacrylate from the dropping tube. A mixture of 0 parts, 45.0 parts of methyl methacrylate and 6.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours and reacted for 3 hours, with a solid content of 60% by weight and a weight average molecular weight. A solution of 9000 acrylic resin was obtained. The acid value of the solid content was 146.3 mgKOH / g.
After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl is prepared so that the non-volatile content is 20% by weight in the previously synthesized resin solution. Etheracetate was added to obtain an acrylic resin solution (B-1) which is an alkali-soluble resin.

<< Preparation of acrylic resin solutions B-1 to 9 >>
Resin solutions B-2 to B-9 corresponding to the resin (B) solution were prepared in the same manner as the resin solution B-1 at the ratios shown in Table 1, respectively. Table 1 shows the results of calculating the weight average molecular weight and the acid value of the solid content.

<< Manufacturing method of miniaturized pigment >>
(Red refined pigment (PR254-1))
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , 190 copies of PR254-1 were obtained.

(Red refined pigment (PR177-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 C.I. I. PR177-1 was obtained in the same procedure as the preparation of PR254-1, except that it was replaced with Pigment Red 177.

(Yellow miniaturized pigment (PY138-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 yellow pigment C.I. I. Pigment Yellow 138 (BASF "Pariotor Yellow L 0962 HD") was used to obtain PY138-1 in the same procedure as for the preparation of PR254-1.

(Yellow refined pigment (PY231-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 yellow pigment C.I. I. PY231-1 was obtained in the same procedure as the preparation of PR254-1, except that it was replaced with Pigment Yellow 231.

(Green miniaturized pigment (PG58-1))
Diketopyrrolopyrrole red pigment C.I. I. PG58-1 was obtained in the same procedure as the preparation of PR254-1, except that Pigment Red 254 was replaced with a halogenated zinc phthalocyanine green pigment (CI Pigment Green 58).

(Green miniaturized pigment (PG62-1))
To a three-necked flask, add 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (7), 500 parts of N-methylpyrrolidone, and 13.9 parts of diphenyl phosphate, and heat to 90 ° C. The reaction was carried out for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain PG62-1, which is a phthalocyanine pigment.

(Green miniaturized pigment (PG63-1))
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (7), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred. The reaction was carried out at 20 ° C. for 6 hours. Then, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added, and the mixture was stirred at 80 ° C. for 1 hour. Then, the mixture was collected by filtration, washed with water, and dried to obtain a pigment in which an average of 10.1 bromine atoms were substituted on the phthalocyanine ring.
Next, to a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment in which an average of 10.1 bromine atoms were substituted on the obtained phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added, and 90 parts were added. It was heated to ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain PG63-1 which is a phthalocyanine pigment.

Equation (7)

<< Adjustment method of pigment dispersant solution >>
The pigment dispersant (“BYK21116” manufactured by Big Chemie) was diluted with propylene glycol monomethyl ether acetate to prepare a pigment dispersant solution having a non-volatile content of 30% by weight.

<Manufacturing method of pigment dispersion>
(Pigment dispersion (PR-1))
After uniformly stirring and mixing 25.0 parts of a red finely divided pigment (PR254-1), 20.0 parts of a pigment dispersant solution, and 55.0 parts of ethylene glycol monomethyl ether acetate, zirconia beads having a diameter of 0.5 mm are used. Was dispersed in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 3 hours and then filtered through a 5 μm filter to obtain a pigment dispersion (PR-1) of PR254.

<< Production of PR-2, PY-1 to 2, PG-1 to 3 >>
Pigment dispersions PR-2, PY-1 to 2, and PG-1 to 3 were prepared in the same manner as the pigment dispersion PR-1 at the ratios shown in Table 2, respectively.

［実施例１］
（着色組成物（Ｒ−Ｇ１））
下記の混合物を均一になるように攪拌混合した後、１．０μmのフィルタで濾過して、着色組成物（Ｒ−Ｇ１）を得た。

ＰＧ−１ ：３０．０部
ＰＹ−１ ：１０．０部
アクリル樹脂溶液（Ｂ−１） ：１０．０部
光重合単量体（Ｃ） ：１５．０部
東亞合成社製「アロニックス Ｍ−４０３」
光重合開始剤（Ｄ） ： ２．０部
ＢＡＳＦ社製「イルガキュア９０７」
チオール化合物（Ｅ） ：０．０２部
ＳＣ有機化学社製「ペンタエリスリトール テトラキス（３−メルカプトプロピオネート）」
溶剤 ：３３．０部
プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）

[Example 1]
(Coloring composition (R-G1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a colored composition (R-G1).

PG-1: 30.0 parts PY-1: 10.0 parts Acrylic resin solution (B-1): 10.0 parts Photopolymerization monomer (C): 15.0 parts Toagosei Co., Ltd. "Aronix M-" 403 "
Photopolymerization Initiator (D): 2.0 parts BASF's "Irgacure 907"
Thiol compound (E): 0.02 part SC "Pentaerythritol tetrakis (3-mercaptopropionate)" manufactured by SC Organic Chemistry Co., Ltd.
Solvent: 33.0 parts Propylene glycol monomethyl ether acetate (PGMEA)

<< Examples 1 to 11 and Comparative Examples 1 to 5 >>
(Coloring composition (R-G2-15, R-R1-2)
The pigment dispersion, the acrylic resin solution, the photopolymerization monomer, the photopolymerization initiator, and the coloring composition (R-G1) except that the types and blending amounts (parts by weight) of the solvent were changed as shown in Table 3. Coloring compositions (R-G2-15, R-R1-2) were obtained in the same manner.

<Evaluation of coloring composition>
The coating film of the obtained coloring composition (coloring compositions (R-G1 to 15, R-R1 to 2) was tested by the following method. The results of the test are shown in Table 4.

<Evaluation of crystal precipitation of coloring composition>
Examples 1 to 11 (colored compositions (R-G1-10, R-R1) and Comparative Examples 1 to 5 (colored compositions (R-G11 to 15, R-R2)) were 100 mm × 100 mm, 0. The coloring compositions of Examples and Comparative Examples were applied onto a 7 mm glass substrate so as to have a film thickness of 2.5 μm, and exposed to ultraviolet rays through a mask having a predetermined pattern. Then, an alkaline developer was sprayed. The desired pattern was formed by spraying to remove the uncured part. The obtained coating film was heat-treated (post-baked) for 60 minutes in an oven at each temperature, and the presence or absence of precipitates was confirmed with an optical microscope. The film thickness was evaluated according to the following criteria. The film thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).

In addition, the heat resistance was evaluated according to the following rank. ◎ is a very good level, 〇 is a good level, and × is a level that is not suitable for practical use.

◎: No precipitation at 270 ° C 〇: No precipitation at 250 ° C, precipitation at 270 ° C ×: Precipitation at 250 ° C or lower

From Table 4, according to the present invention, the colorant (A) is a colorant containing a colorant (A1) having a quinophthalone skeleton and a colorant (A2) having a diketopyrrolopyrrole skeleton, and is represented by the general formula (1). The coloring composition for a color filter using the resin (B) and the thiol compound (E) having an acid value of 100 to 170 mgKOH / g according to the constituent units showed excellent results in suppressing crystal precipitation.
Among them, the suppression of crystal precipitation of the coloring composition using the resin (B) and the thiol compound (E) having an acid value of 125 to 150 mgKOH / g according to the structural unit represented by the general formula (1) was particularly excellent. ..

Further, from the above results, the colorant (A) is represented by the general formula (1) as a colorant containing a colorant (A1) having a quinophthalone skeleton and a colorant (A2) having a diketopyrrolopyrrole skeleton. It was confirmed that by using the resin (B) and the thiol compound (E) having an acid value of 100 to 170 mgKOH / g depending on the constituent unit, it is possible to provide a color filter excellent in suppressing crystal precipitation.

Claims (4)

A coloring composition containing a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and a polyfunctional aliphatic thiol compound.
The resin (B) has a structural unit represented by the following general formula (1), and the acid value derived from the structural unit represented by the following general formula (1) is 112.1 to 146.3 mgKOH / g. , and the colorant (a) is seen containing a coloring agent (A2) having a colorant (A1) or diketopyrrolopyrrole backbone having a quinophthalone backbone, the photopolymerization initiator (D) is acetophenone photopolymerization initiator , Benzoin-based photopolymerization initiator, benzophenone-based photopolymerization initiator, thioxanson-based photopolymerization initiator, triazine-based photopolymerization initiator, borate-based photopolymerization initiator, carbazole-based photopolymerization initiator, and imidazole-based photopolymerization initiator. A coloring composition for a color filter, which is a photopolymerization initiator selected from the group consisting of.

General formula (1)

[In the general formula (1), R ₁ , R ₂ , and R ₃ are each independently of −H or −CH ₃ , and R ₄ is.

R ₅ is − (CH ₂ ) _n −, −C ₆ H ₄ −, −C ₆ H ₁₀ −, −C ₂ H ₂ −,
, And m and n are integers of 1 to 4. The coloring composition for a color filter according to claim 1, wherein the coloring agent (A) contains a coloring agent (A1) having a quinophthalone skeleton. A color filter comprising a filter segment formed by using the coloring composition for a color filter according to claim 1 or 2. A liquid crystal display device comprising the color filter according to claim 3.