JP2018141894A - Coloring composition for color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide 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 filter formed by using the coloring composition for a color filter. It is to be. SOLUTION: The above-mentioned problem is a coloring composition containing a colorant, a resin, a photopolymerizable monomer, a photopolymerization initiator and a thiol compound, and the resin has a specific structure. The acid value derived from the structural unit having a structural unit and having a specific structure is 100 to 170 mgKOH / g, and the colorant contains a colorant having a quinophthalone skeleton or a colorant having a diketopyrrolopyrrole skeleton. It is solved by a coloring composition for a color filter characterized by. [Selection diagram] None

Description

  The present invention relates to a color liquid crystal display device, a color composition for color filter used in the production of a color filter used in a color imaging device, 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.

  In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive into a resin in which pigment particles as a colorant are dispersed in a resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. In this method, a color filter is produced by forming a coating film by the above, performing selective exposure through a mask with an aligner or a stepper, patterning by alkali development and thermosetting, and repeating this operation.

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

  If a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend. Furthermore, as described above, since the color liquid crystal device has been used for televisions, personal computer monitors, and the like, the demand for high reliability and high lightness and contrast for color filters has also increased.

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

  However, although diketopyrrolopyrrole pigments and quinophthalone pigments are excellent in lightness, there is a problem in heat resistance when they are used finely. In recent years, there has been a strong demand for high contrast for color filters. For this purpose, it is necessary to make the primary particle diameters of diketopyrrolopyrrole pigments and quinophthalone pigments as fine as possible. However, there is a problem that the diketopyrrolopyrrole pigment and the quinophthalone pigment that have been refined are crystallized and precipitated in the heating step when forming the color filter.

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

JP-A-2006-105169 (FUJIFILM resin-linked quinophthalone synthesis) JP-A-2006-035068 (FUJIFILM resin-linked quinophthalone synthesis) JP-A-2006-145282 (Toyo Ink Quinophthalone Skeleton Synthesis) International Publication No. 2009/081930 Pamphlet JP 2009-149707 A

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

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

That is, the present invention provides a colored 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 an acid value derived from the structural unit represented by the following general formula (1) is 100 to 170 mgKOH / g. And the colorant (A) contains a colorant (A1) having a quinophthalone skeleton or a colorant (A2) having a diketopyrrolopyrrole skeleton.

General formula (1)

[In General Formula (1), R ₁ , R ₂ , and R ₃ are each independently —H or —CH ₃ , and R ₄ is

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

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

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

  The present invention also relates to a liquid crystal display device comprising the color filter.

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

Hereinafter, embodiments of the present invention will be described in detail.
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” in this specification means a color index (CI).

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

<Coloring composition for color filter>
<< Colorant (A) >>
The colorant (A) of the present invention contains a quinophthalone pigment that is a colorant (A1) having a quinophthalone skeleton or a diketopyrrolopyrrole pigment that is a colorant (A2) having a diketopyrrolopyrrole skeleton. Mainly green or yellow or red color filter pixels can be made using the inventive colored composition.

<Quinophthalone pigment (A1)>
The quinophthalone pigment of the present invention is a known pigment such as C.I. I. Pigment yellow 138, C.I. I. And CI Pigment Yellow 231. The quinophthalone pigment also includes the following general formula (4). The content of the quinophthalone pigment is preferably 10 to 70 parts by weight as 100 parts by weight of the colorant.
General formula (4)

[In 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, or 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 A good phthalimidomethyl group or a sulfamoyl group which may have a substituent is shown. However, the 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 ptyl group, an isoptyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group. Group, stearyl group, linear or branched alkyl group such as 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 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-butylbenzyl group, 4-methoxy Examples thereof include an alkyl group having a substituent such as a pendyl 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-butyloxy 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, 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 include an alkoxyl group having a substituent such as a propoxy group and a benzyloxy group.

  In addition, examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group, an anthranyl group, a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, 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 a substituent.

Examples of acidic groups include —SO ₃ H and —COOH, and monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, and aluminum salts. Etc. In addition, as the alkyl ammonium salt of acidic group, quaternary alkyl such as ammonium salt of long-chain monoalkylamine such as octylamine, laurylamine, stearylamine, palmityltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salt, etc. An ammonium salt is mentioned.

The “substituent” in the phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) which may have a substituent and the sulfamoyl group (H ₂ NSO ₂ —) which may have a substituent "Includes the above 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.

  The adjacent groups of X1 to X4 and / or X10 to X13 of the general formula (4) are combined to form an aromatic ring which may have a substituent. The aromatic ring herein includes a hydrocarbon aromatic ring and a heteroaromatic ring. The hydrocarbon aromatic ring includes a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, and the heteroaromatic ring includes pyridine. A ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline 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 such as 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, C.I. I. It is most preferable to use Pigment Red 254 because it has high brightness. The content of the diketopyrrolopyrrole pigment is preferably 60 to 90 as 100 parts by weight of the colorant.
(Other colorants)
Moreover, as another coloring agent which can be used for the coloring composition of this invention, it can select arbitrarily from a conventionally well-known various pigment and dye. 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 organic pigments include azo pigments such as azo, disazo, or polyazo, anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, or violanthrone, quinacridone pigments, Examples thereof include perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium 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 do. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Green 7, 36, 58, 62 or 63. Moreover, the zinc phthalocyanine pigments described in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like can also be used, and the invention is not particularly limited thereto.

Specifically, as these organic pigments,
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, 256, 257, 258, 259, 260, 262, 263, 265, 266, 267, 268, 269, 270, 271, 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 177, C.I. I. It is particularly preferable to use CI Pigment Red 269.

In the coloring composition of the present invention, yellow pigments can be used as green, yellow and red toning pigments.
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.

  The content of the colorant is preferably 10% by weight or more, more preferably 15% by weight or more from the viewpoint of obtaining sufficient color reproducibility, based on the total nonvolatile components of the coloring composition (100% by weight), and most preferably Preferably it is 20 weight% or more. Further, from the viewpoint of the stability of the coloring composition, the preferred 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, the dye which can be used in combination with the quinophthalone pigment and the diketopyrrolopyrrole pigment in the colored composition of the present invention will be described. Examples of the dyes that can be used in combination include compounds classified as dyes by the Color Index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (Color Dyeing Co., Ltd.). Oil-soluble dyes, acid dyes, metal complex dyes, basic dyes, direct dyes, disperse dyes, mordant dyes, and the like. Of these, oil-soluble dyes, acid dyes, metal complex dyes, and basic dyes are preferred.
Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And 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.
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, or C.
I. Solvent violet 10 etc. are mentioned.

  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.

Anthraquinone oil-soluble dyes include CI Solvent Red 172, 222, C.I.
I. Solvent violet 60 etc. are mentioned.

<Acid dye>
Examples of triarylmethane acid dyes include 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 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.

As the anthraquinone acid dye, 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, direct violet 17 or the like.

Examples of azo acid dyes 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.

[Salt-forming compounds of acid dyes]
The dye used in combination with the quinophthalone pigment and the diketopyrrolopyrrole pigment in the present invention is preferably an acid dye from the viewpoint of heat resistance and light resistance, and a salt-forming compound of an acid dye and a nitrogen-containing compound from the viewpoint of stability. It is more preferable that salt formation is performed 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, to produce a xanthene acid dye. A salt compound is particularly preferable because high heat resistance, light resistance, and solvent resistance can be imparted.
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, thereby reducing the brightness and resistance. It can be set as the outstanding coloring composition.

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

  The resin having a cationic group in the side chain is an alkali 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 the xanthene acid dye. A salt-forming compound can be obtained by forming a salt.

General formula (5)

[In General Formula (5), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ^{52 to} R ⁵⁴ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R ^{52 to} R ⁵⁴ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ⁵⁵ —, —COO—R ⁵⁵ —, and R ⁵⁵ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

"Salt formation with acid dyes"
A salt-forming compound of an acid dye and a resin having a cationic group in the side chain can be produced by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969.
For example, a xanthene acid dye may be used, and after the xanthene acid dye is dissolved in water, a quaternary ammonium salt compound may be added and subjected to chlorination while stirring. Here, the sulfonic acid group (—SO ₃ H) and sodium sulfonate group (—SO ₃ Na) 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.

  Further, 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 (5) and an acidic dye are dissolved, or the general formula (5 ), An aqueous solution of a resin having a cationic group in the side chain and an aqueous solution of an acidic dye can be easily obtained by mixing under stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the acidic 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 acidic dye is water-soluble and can be removed by washing or the like. As for the resin having a cationic group in the side chain to be used and the acid dye, only a single type or a plurality of types having different structures may be used.

<Metal complex dye>
The metal complex dye can be preferably used because it exhibits a fluorescence quenching effect on a pigment having fluorescence.
Examples of the metal complex 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, C.I. 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; 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 exemplified. 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 dyes may be used alone or in combination of two or more.

In addition, when a coloring agent contains dye, it is preferable that content of dye is 1-50 weight part with respect to 100 weight part of pigments. More preferably, it is 20-30 weight part. When the added amount of the dye is within this range, the lightness and contrast ratio, heat resistance and chemical resistance can be improved. In the color filter coloring composition of the present invention, it is preferable that the colorant contains both a pigment and a dye from the above viewpoint.

<Miniaturization of pigment>
When the pigment is used in the present invention, it is preferably used after being refined, but the refinement method is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation can be used, and examples are given in the present invention. Thus, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Further, it is preferably 100 nm or less because a color filter having a high contrast ratio can be formed. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission 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 pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to a cube of the obtained particle size, and the volume average particle size is defined as the average primary particle size.
The colored composition of the present invention is excellent in resistance even when such a finely-treated pigment is used by containing an epoxy compound together with a specific pigment dispersant containing a heat-crosslinkable functional group. In addition, a coloring composition for a color filter having a high luminance and contrast ratio can be obtained.

  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.

<Pigment dispersant>
When dispersing the colorant (A) in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing 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 a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine.
Among these, a pigment derivative is preferable, and the structure thereof is a compound 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 optionally substituted phthalimidomethyl group n: an integer of 1 to 4 is there)
Examples of the organic pigment constituting the organic pigment residue of P include, for example, 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, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. What is currently used can be used, These can be used individually or in mixture of 2 or more types.
The blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, and most preferably 3% by weight or more based on 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, the amount is preferably 40% by weight or less, and most preferably 35% by weight or less with respect to 100 parts by weight of the colorant (A).

The resin-type dispersant has a pigment-affinity part having a 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- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF Manufactured by EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 101,120,150,1501,1502,1503, 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 may be used alone or in admixture of two or more, but are not necessarily limited thereto.

When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant (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 added effect. When the blending amount is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<< Resin (B) >>
The colored composition of the present invention has a structural unit represented by the following general formula (1) and a resin B having an acid value of 100 to 170 mgKOH / g based on the structural 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 General Formula (1), R ₁ , R ₂ , and R ₃ are each independently —H or —CH ₃ , and R ₄ is

And R ₅ is — (CH ₂ ) _n —, —C ₆ H ₄ —, —C ₆ H ₁₀ —, —C ₂ H ₂ —,
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 colored 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. High degree. For this reason, since a quinophthalone pigment or a diketopyrrolopyrrole pigment interacts with an acid group to suppress pigment aggregation due to heating, a highly heat-resistant colored composition free from crystal precipitation can be obtained.

  As the structural unit represented by the general formula (1), in particular, a structural unit represented by the formula (6), a structural unit formed from a 2-hydroxyethyl methacrylate-modified succinic anhydride, a phthalate 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 preferred, and among them, it is formed from a 2-hydroxyethyl methacrylate succinic anhydride modified product. The structural unit is particularly preferred.

Formula (6)

Formula (7)

Formula (8)

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

As other structural units represented by the general formula (1), known polybasic acid anhydrides to be added to the hydroxyl group of the copolymer can be used. Examples thereof include maleic anhydride, succinic anhydride, phthalic anhydride, and hexahydrophthalic anhydride.

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 derived from the structural unit represented by the general formula (1) (mgKOH / g)
= {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)

Resin B of the colored composition of the present invention can have a structural unit derived from another monomer in addition to the structural unit represented by the general formula (1). 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. Styrene, α-methylstyrene, vinyl toluene, vinyl acetate, vinyl propionate, acrylic acid, acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, monohydroxyethyl acrylate phthalate, maleic acid, itaconic acid, fumaric acid, Glutaconic acid, tetrahydrophthalic acid, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Droxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin (meth) acrylate, polycaprolactone-modified hydroxyethyl (meth) acrylate (repetition number of caprolactone = 1 to 6), Examples thereof include, but are not limited to, ethylenically unsaturated monomers such as epoxy (meth) acrylate and hydroxyl-terminated urethane (meth) acrylate. Moreover, 1 type, or 2 or more types can be used for these.

<< Photopolymerizable monomer (C) >>
The photopolymerizable monomer (C) is one that is cured by ultraviolet rays or heat to produce 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 from the viewpoint of photocurability and developability. More preferably, it is 300 parts by weight.
Examples of the photopolymerizable monomer (C) used in the color filter coloring composition 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 diglycid Ruether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, Various acrylic esters and methacrylic esters such as epoxy (meth) acrylate and urethane acrylate, (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. Not.

<< 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-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenone photopolymerization initiators such as -1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 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 (trick (Romethyl) -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, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used.

  These photopolymerization initiators are used alone or in admixture of two or more. As a sensitizer, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl-9,10-phenanth Such as lenquinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. A compound can also be used in combination. The sensitizer can be used in an amount of preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

<< thiol compound (E) >>
The coloring composition for a color filter of the present invention contains a thiol compound (E). By using the thiol compound (E) together with the above-described photopolymerization initiator, in the radical polymerization process after irradiation with light, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated. The coloring composition for use is highly crosslinked. For this reason, the pigment in the coloring composition is captured, and at the same time, the reduction of the momentum of the pigment also tends to cause an interaction with the acid group of the structural unit represented by the general formula (1), thereby suppressing heat aggregation and heat resistance. The 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 is preferable.

Examples of the thiol compound (E) include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiol. Propionate, Trimethylolpropane tristhioglycolate, Trimethylolpropane tristhiopropionate, Trimethylolethane tris (3-mercaptobutyrate), Trimethylolpropane tris (3-mercaptobutyrate), Trimethylolpropane tris ( 3-mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopro Onate), dipentaerythritol hexakis (3-mercaptopropionate), tris (2-hydroxyethyl) isocyanurate, trimercaptopropionic acid, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s- Examples include triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine.
These thiol compounds (E) can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

As for content of a thiol compound (E), 0.05-10 weight part is preferable with respect to 100 weight part of resin (B), More preferably, it is 0.1-5.0 weight part.
By using 0.05 part by weight or more of the thiol compound (E), the crosslinking point of the colored composition is increased, and a colored composition with higher heat resistance and suppressed crystal precipitation can be obtained.

"Organic solvent"
The organic solvent is a filter in which a colorant is sufficiently dispersed in a transparent resin, and the colored composition of the present invention is applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. 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).
As the organic solvent, 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-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3- Methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, P-chlorotoluene, P-diethylbenzene, seC-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone , Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol 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 glycol monobutyl ether, dipropylene glycol Propyl 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, methylcyclohexanol, n-amyl acetate, acetic acid - butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters and the like. These may be used singly or in combination.

《Other additives》
In the coloring composition for a color filter of the present invention, a dispersion aid such as a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing re-aggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in a transparent resin using the dispersion aid was used. In this case, a color filter having excellent transparency can be obtained. The dispersing 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 dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines These may be used alone or in combination of two or more.

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

<< Method for Producing Colored Composition for Color Filter >>
The coloring composition for a color filter of the present invention comprises a kneader, a two-roll mill, a three-roll mill, and a ball mill in a colorant carrier such as a resin and / or a solvent, if necessary, together with a dispersion aid. Further, it can be produced by finely dispersing using various dispersing means such as a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.
When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need.

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

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

《Color filter manufacturing method》
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

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

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

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, etc. in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . 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 this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention 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. Unless otherwise specified, “parts” and “%” mean “parts by weight” and “% by weight”.

  Moreover, the measuring method of the weight average molecular weight (Mw) of resin and the calculation method of the acid value (mgKOH / g) of resin are as follows.

<< 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).

<< 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 the acid value of the carboxyl group-containing unsaturated monomer (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, A method for producing the dye-containing solution will be described.

<< Method for Producing 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))
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 194.0 parts of propylene glycol monoethyl ether acetate, heated to 80 ° C., and the inside of the reaction vessel was filled with nitrogen. After the 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. 0 parts, 45.0 parts of methyl methacrylate and 6.0 parts of 2,2′-azobisisobutyronitrile were added dropwise over 2 hours and reacted for 3 hours, solid content 60% by weight, weight average molecular weight A solution of 9,000 acrylic resins was obtained. The acid value of solid content was 146.3 mgKOH / g.
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.

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

<< Method for producing refined 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 into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of PR254-1.

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

(Yellow refined pigment (PY138-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 is changed to yellow pigment C.I. I. PY138-1 was obtained by the same procedure as that for the preparation of PR254-1, except that it was replaced with CI Pigment Yellow 138 (BASF “PAliotol Yellow L 0962 HD”).

(Yellow refined pigment (PY231-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 is changed to yellow pigment C.I. I. Except having replaced with pigment yellow 231, PY231-1 was obtained in the same procedure as preparation of PR254-1.

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

(Green refined 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 allowed for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain PG62-1, which is a phthalocyanine pigment.

(Green refined pigment (PG63-1))
In 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. Thereafter, 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 stirred at 80 ° C. for 1 hour. Thereafter, the mixture was collected by filtration, washed with water, and dried to obtain a pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 10.1 bromine atoms substituted on the resulting phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain PG63-1, which is a phthalocyanine pigment.

Formula (7)

<Method for adjusting pigment dispersant solution>
A pigment dispersant ("BYK21116" manufactured by Big Chemie) 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 (PR-1))
After uniformly stirring and mixing 25.0 parts of the red refined pigment (PR254-1), 20.0 parts of the pigment dispersant solution, and 55.0 parts of ethylene glycol monomethyl ether acetate, zirconia beads having a diameter of 0.5 mm Then, the mixture was dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then filtered through a 5 μm filter to obtain a PR254 pigment dispersion (PR-1).

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

[Example 1]
(Coloring composition (R-G1))
The following mixture was stirred and mixed 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 photopolymerizable monomer (C): 15.0 parts “Aronix M-” manufactured by Toagosei Co., Ltd. 403 "
Photopolymerization initiator (D): 2.0 parts "Irgacure 907" manufactured by BASF
Thiol compound (E): 0.02 part "Pentaerythritol tetrakis (3-mercaptopropionate)" manufactured by SC Organic Chemical Co., Ltd.
Solvent: 33.0 parts Propylene glycol monomethyl ether acetate (PGMEA)

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

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

<Evaluation of Crystal Precipitation of Colored Composition>
About Examples 1-11 (colored compositions (R-G1-10, R-R1)) and Comparative Examples 1-5 (colored compositions (R-G11-15, R-R2)), 100 mm × 100 mm, 0. The colored composition in each example and comparative example was applied on a 7 mm glass substrate so as to have a film thickness of 2.5 μm, and then exposed to ultraviolet rays through a mask having a predetermined pattern. Sprayed to remove the uncured part to form the desired pattern.The obtained coating film was subjected to heat treatment (post bake) 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 of the coating film was determined using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).

Moreover, it evaluated by the following rank as heat resistance. ◎ is a very good level, ◯ is a good level, and x is a level not suitable for practical use.

◎: No precipitation at 270 ° C. ○: No precipitation at 250 ° C. ×: Precipitation at 270 ° C. ×: Precipitation at 250 ° C. or less

From Table 4, it is represented by the general formula (1) in the colorant containing the colorant (A1) having a quinophthalone skeleton and the colorant (A2) having a diketopyrrolopyrrole skeleton. The color composition for color filters using the resin (B) having an acid value of 100 to 170 mgKOH / g and the thiol compound (E) according to the structural unit showed excellent results in suppressing crystal precipitation.
Especially, the crystal | crystallization precipitation suppression of the coloring composition using the resin (B) whose acid value by the structural unit represented by General formula (1) is 125-150 mgKOH / g, and the thiol compound (E) was especially excellent. .

  From the above results, the colorant (A) is represented by the general formula (1) in the colorant containing the colorant (A1) having a quinophthalone skeleton and the 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 based on the structural unit, a color filter can be provided with excellent crystal precipitation suppression.

Claims (4)

A coloring composition comprising a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and a thiol compound (E), wherein the resin (B) has a structural unit represented by the following general formula (1), and an acid value derived from the structural unit represented by the following general formula (1) is 100 to 170 mgKOH / g, and a colorant ( A color composition for a color filter, wherein A) comprises a colorant (A1) having a quinophthalone skeleton or a colorant (A2) having a diketopyrrolopyrrole skeleton.

General formula (1)
[In General Formula (1), R ₁ , R ₂ , and R ₃ are each independently —H or —CH ₃ , and R ₄ is
And R ₅ is — (CH ₂ ) _n —, —C ₆ H ₄ —, —C ₆ H ₁₀ —, —C ₂ H ₂ —,
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 using the coloring composition for a color filter according to claim 1.   A liquid crystal display device comprising the color filter according to claim 3.