JP2017097173A - Colored composition for color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition for a color filter, which suppresses crystallization even in a heat treatment at 200°C or higher in the process of manufacturing a color filter and shows excellent developability of a photosensitive colored composition, and a color filter having high lightness formed by using the above colored composition for a color filter.SOLUTION: The colored composition for a color filter comprises a colorant, a binder resin, a nitrogen-containing five-membered cyclic compound and an organic solvent.SELECTED DRAWING: 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.

  Light filter such as diketopyrrolopyrrole pigment, anthraquinone pigment, perylene pigment or disazo pigment as a colorant for the red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate In general, pigments excellent in heat resistance and heat resistance are used alone or in combination.

  Among the diketopyrrolopyrrole pigments, C.I. I. Pigment Red 254 is widely used. However, although the pigment is excellent in lightness, there is a problem in heat resistance when it is used after being miniaturized. 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 size of diketopyrrolopyrrole pigments as fine as possible. However, since the diketopyrrolopyrrole pigments that have been refined have the property of being easy to grow crystals due to their intermolecular hydrogen bonds, crystallization occurs in the heating process when forming the color filter, and foreign matter is generated. Is a problem.

Patent Document 1 and Patent Document 2 include diketopyrrolopyrrole pigments (mainly CI Pigment Red 254) and at least one diaryl diketopyrrolopyrrole compound having a specific structural formula. And a pigment derivative are used in combination, and a coloring composition for a color filter is disclosed in which crystal precipitation due to high contrast and heating process is suppressed. However, although these methods have improved the crystal precipitation to some extent, they have not yet been completely suppressed, and there are problems such as a decrease in lightness and deterioration of developability due to the addition of derivatives. Improvement is desired.

International Publication No. 2009/081930 Pamphlet JP 2009-149707 A

  An object of the present invention is to provide a color filter coloring composition that suppresses crystal precipitation even in a heat treatment at 200 ° C. or higher in the color filter manufacturing process and is excellent in developability of the photosensitive coloring composition, and coloring for the color filter To provide a color filter with high brightness formed using the composition.

  As a result of intensive investigations to solve the above problems, the present inventors have significantly improved heat resistance and developability of the color filter coloring composition containing a nitrogen-containing five-membered ring compound having a specific structure. The present inventors have found that a color filter with high brightness can be obtained.

That is, the present invention is a coloring composition containing a colorant (A), a binder resin (B), and a nitrogen-containing five-membered ring compound (C), wherein the colorant (A) is diketopyrrolo. A linear alkyl group or alkylene group having 1 to 20 carbon atoms is directly bonded to at least one nitrogen atom of the five-membered ring portion of the nitrogen-containing five-membered ring compound (C), which contains a pyrrole pigment. The present invention relates to a coloring composition for a color filter.

  The present invention also relates to a coloring composition for a color filter, wherein the nitrogen-containing five-membered ring compound (C) has a molecular weight of 100 to 1,000.

  In the present invention, the content of the nitrogen-containing five-membered ring compound (C) is 1 to 20 parts by weight with respect to 100 parts by weight of the diketopyrrolopyrrole pigment contained in the colorant (A). The present invention relates to a colored composition for a color filter.

The present invention also relates to a color filter coloring composition comprising a polyfunctional monomer and / or a photopolymerization initiator.

  The present invention also relates to a color filter comprising a filter segment formed on the base material from the color filter coloring composition.

  Even when heat treatment at 200 ° C. or higher in the color filter manufacturing process is performed with the colored composition for a color filter of the present invention, a high brightness filter segment can be formed without precipitation of crystals. In addition, it has excellent fastness such as heat resistance and chemical resistance, and also has good stability and developability. Therefore, a color liquid crystal display device with low power consumption and high quality can be manufactured using this color filter.

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 contains a colorant, a binder resin, a nitrogen-containing five-membered ring compound, 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 diketopyrrolopyrrole pigment, and a pixel of a red color filter can be made using the colored composition of the present invention.
(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. What is the content of the diketopyrrolopyrrole pigment? 60-90 are preferable as 100 weight part of coloring agents.
(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.

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, a yellow pigment can be used as a red toning pigment.
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 that can be used in combination with the diketopyrrolopyrrole 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>
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 25, 27, Direct Violet 17, and 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 diketopyrrolopyrrole pigment in the present invention is preferably an acid dye from the viewpoint of heat resistance and light resistance, and more preferably a salt-forming compound of an acid dye and a nitrogen-containing compound from the viewpoint of stability. Preferably, chlorination 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 form a salt formation compound of a xanthene acid dye. It is particularly preferable because it can provide 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, 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 (1), and the cationic group in the general formula (1) is an anionic group of the xanthene acid dye. A salt-forming compound can be obtained by forming a salt.

General formula (1)

[In General Formula (1), 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.

  In addition, 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 (1) and an acidic dye are dissolved, or the general formula (1 ), 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, with respect to 100 or more pigment particles, the volume of each particle is obtained by approximating it with 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, based on 100 parts by weight of the pigment, from both the processing efficiency and the 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 with respect to 100 parts by weight of the colorant (A) from the viewpoint of improving dispersibility. is there. Further, from the viewpoint of heat resistance and light resistance, 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. May affect.

<< Binder resin (B) >>
The coloring composition for a color filter of the present invention contains a binder resin. By including a binder resin, the dispersion stability of the colored composition of the present invention becomes better, and when a colored pixel layer of a color filter is formed using the colored composition for a color filter, development with less pigment aggregates A colored pixel layer with good properties and pattern shape can be obtained.

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.
Further, a thermoplastic resin is preferable, and when used in the form of an alkali developing type colored resist material, it is preferable to use an alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.
In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. This is more preferable because the photocuring density is increased, and as a result, resistance is improved.

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

Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

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

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

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

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

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g from the viewpoints of dispersibility, penetrability, developability, and resistance of the pigment. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  Since the binder resin has good film formability and various resistances, it is preferably used in an amount of 20 parts by weight or more with respect to 100 parts by weight of the colorant, because the colorant concentration is high and good color characteristics can be expressed. , And preferably used in an amount of 1000 parts by weight or less.

<Nitrogen-containing five-membered ring compound (C)>
The nitrogen-containing five-membered ring compound (C) in the present invention is characterized in that a linear alkyl group or alkylene group having 1 to 20 carbon atoms is directly bonded to at least one nitrogen atom of the five-membered ring portion. .
The nitrogen-containing five-membered ring compound in the present invention is a compound having at least one nitrogen atom in the five-membered ring portion, and examples thereof include imidazole compounds, pyrrole compounds, pyrrolidine compounds, pyrazole compounds, and the like. The nitrogen-containing five-membered ring compound (C) is further characterized in that a linear alkyl group or alkylene group having 1 to 20 carbon atoms is directly bonded to at least one nitrogen atom of the five-membered ring portion.
Specifically, 1-vinylimidazole, 1-methylpyrrole, 1,2-dimethylimidazole, 1-ethyl-3-methylimidazolium hexafluorophosphate, N-methyl-N-propylpyrrolidinium bis (trifluoromethanesulfonyl) Imide), 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide, and the like.

Moreover, as for carbon number of the linear alkyl group or alkylene group couple | bonded directly with a nitrogen atom, 2-10 are preferable.

  In addition, the molecular weight of the nitrogen-containing five-membered ring compound in the present invention is preferably 100 to 1,000, and if it is less than 100, it is not preferable from the viewpoint of the pattern remaining film ratio, and it exceeds 1,000 like a resin. Is not preferable from the viewpoint of developability.

In addition, the content of the nitrogen-containing five-membered ring compound in the present invention is 1.0 to 20.0 parts by weight with respect to 100 parts by weight of the diketopyrrolopyrrole pigment contained in the colorant (A). Is preferred. More preferably, it is 10.0 or more and less than 15.0 parts by weight. If it is 10.0 parts by weight or more, it is excellent in suppressing crystal precipitation, and if it exceeds 20.0 parts by weight, the shape of the pattern cross section is not preferable in developability.

Particularly preferred conditions for the nitrogen-containing five-membered ring compound used in the present invention include a straight-chain alkyl group or alkylene group having 2 to less than 10 carbon atoms directly bonded to at least one nitrogen atom of the five-membered ring portion, and a molecular weight of 100 to 1,000. Examples of the nitrogen-containing five-membered ring compound that satisfies all these conditions include 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide, and the like.

A coloring composition having a finely-divided diketopyrrolopyrrole pigment that has been developed conventionally grows crystals upon heating due to intermolecular hydrogen bonding between the pigments, and the generation of foreign matters appears remarkably.
Since the nitrogen-containing five-membered ring compound used in the present invention has a structure similar to a part of the diketopyrrolopyrrole pigment, it is presumed that the surface of the pigment can be covered. Furthermore, it is considered that intermolecular hydrogen bonding between the above pigments is inhibited by using a nitrogen-containing five-membered ring compound in which a linear alkyl group or alkylene group is directly bonded to a nitrogen atom. Thereby, it is considered that crystal growth of the diketopyrrolopyrrole pigment due to heating can be suppressed, foreign matter generation can be suppressed, and a coating film having high heat resistance can be formed.
Furthermore, the pigment dispersion stability can be improved by setting the straight-chain alkyl group or alkylene group directly bonded to the nitrogen atom to 20 or less carbon atoms.

《Polyfunctional monomer》
Multifunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane Polyfunctional monomers having an acidic group, such as various acrylic esters and methacrylic esters such as tri (meth) acrylate, or photopolymerizable monomers whose polymerization is induced by radicals can be raised.

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

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

<< Photopolymerization initiator >>
As photopolymerization initiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) -butan-1-one and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Compound, benzoin, benzoin methyl ether, benzoin ethyl ether, ben Benzoin compounds such as inisopropyl ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethyl Thioxanthone compounds such as thioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-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-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4- Triazine compounds such as trichloromethyl (4′-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-ben) Oxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and the like, bis (2,4,6- Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl -1,2'-biimidazole, 2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ′, 5,5′-tetra (p-methylphenyl) biimidazole, imidazole compounds, 9,10-phenanthrenequinone, camphor -Quinone compounds such as quinone and ethyl anthraquinone, borate compounds, carbazole compounds, titanocene compounds and the like are used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

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

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

<Sensitizer>
A sensitizer can be contained in the coloring composition for a color filter of the present invention.
As sensitizers, unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline Derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives , Tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spiro Oxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler ketone derivatives, and the like can be given.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

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

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

"solvent"
In the coloring composition for a color filter of the present invention, the coloring agent is sufficiently dispersed in a dye carrier such as a binder resin or a polyfunctional monomer, and the dry film thickness is 0.2 to 10 μm on a transparent substrate such as a glass substrate. It is used for facilitating application to form a filter segment or a black matrix.

Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butylal N-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Recall monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether , Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl Tons, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  A solvent can be used in the quantity of 100-10000 weight part with respect to 100 weight part of coloring agents in a coloring composition, Preferably it is 500-5000 weight part.

《Polyfunctional thiol》
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups.
By using polyfunctional thiol together with the above-mentioned photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates a thiyl radical that is less susceptible to polymerization inhibition by oxygen. The composition becomes highly sensitive. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate) ), Dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s- Examples include triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine.
These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the colorant.
By using 0.05 part by weight or more of polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

《Leveling agent》
In order to improve the leveling property of the composition on the transparent substrate, a leveling agent is added to the colored composition of the present invention, and the leveling agent is preferably dimethylsiloxane having a polyether structure or a polyester structure in the main chain. . Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 1.0 part by weight with respect to 100 parts by weight of the total weight of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

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

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

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

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

"Antioxidant"
The colored composition for a color filter of the present invention can contain an antioxidant in order to increase the transmittance of the coating film. The antioxidant is a coating film for preventing the resin [B] and the photopolymerization initiator [E] contained in the color filter coloring composition from being oxidized and yellowed by a thermal process during thermal curing or ITO annealing. The transmittance of can be increased. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

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

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5- And di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

  In the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N , N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4- Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3,4 -Butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6- Tetramethyl-4-piperidyl) Mino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2,2 , 6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) -4 Polycondensate with -hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine and the like.

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

  As sulfide-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like.

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

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

  Examples of the silane coupling agent include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy (Cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-amino Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Examples include aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant [A] in the coloring composition.

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

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

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

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

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

  Subsequently, a method for producing an acrylic resin solution used in Examples and Comparative Examples, a method for producing a resin having a cationic group in a side chain, a method for producing a micronized pigment, a method for preparing a pigment dispersant solution, and a pigment dispersion The method for producing the dye, the method for producing the salt-forming compound of the dye, the method for producing the dye-containing solution, the structure / property values of the nitrogen-containing five-membered ring compound (C), etc.

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

<Method for producing resin having cationic group in side chain>
(Resin 1 having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 62.4 parts of isopropyl alcohol was charged and heated to 75 ° C. under a nitrogen stream. Separately, 32.1 parts of ethyl methacrylate, 25.1 parts of n-propyl methacrylate, 25.1 parts of lauryl methacrylate, 17.7 parts of methacryloylaminopropyltrimethylammonium chloride, 2,2′-azobis (2,4-dimethylvaleronitrile 5.7) and 15.6 parts of methyl ethyl ketone were made uniform, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain Resin 1 having a cationic group in the side chain whose resin component was 40% by weight. The ammonium salt value of the obtained resin was 45 mgKOH / g.

<Method for producing refined pigment>
(Red refined pigment (PR-1))
Red pigment C.I. I. Pigment Red 254 (PR254) (BASF “Irgafore Red B-CF”) 152 parts, 8 parts of the pigment derivative of the chemical formula (2), 1600 parts of sodium chloride, and 190 parts of diethylene glycol 1 gallon kneader (Inoue Seisakusho) And kneaded at 60 ° C. for 10 hours. Next, the mixture is poured into 3 liters of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and solvent, and then 80 It was dried for 1 day at 0 ° C. to obtain a red refined pigment (PR-1). The average primary particle diameter of the obtained pigment was 35 nm.

Chemical formula (2)

(Red refined pigment (PR-2))
Red pigment C.I. I. 500 parts of Pigment Red 177 (PR177) (“chromophthaled red A2B” manufactured by BASF), 3500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. . Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a red-refined pigment (PR-2) was obtained. The average primary particle diameter of the obtained pigment was 30 nm.

(Red refined pigment (PR-3))
Red pigment C.I. I. 100 parts of Pigment Red 269 (PR269), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product was put into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. Thus, a red refined pigment (PR-3) was obtained. The average primary particle diameter of the obtained pigment was 35 nm.

(Purple refinement treatment pigment (PV-1))
Dioxazine-based purple pigment C.I. I. 500 parts of Pigment Violet 23 (PV23) (“Fast Violet RL” manufactured by Clariant), 2500 parts of sodium chloride, and 250 parts of polyethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 120 ° C. for 12 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, Drying at 80 ° C. for a whole day and night gave a purple finely treated pigment (PV-1). The average primary particle diameter of the obtained pigment was 30 nm.

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

<Method for producing pigment dispersion>
(Pigment dispersion (P-R1))
After uniformly stirring and mixing 12 parts of the red micronized pigment (PR-1), 33 parts of the acrylic resin solution (B-1), 5 parts of the pigment dispersant solution, and 50 parts of ethylene glycol monomethyl ether acetate, Using 5 mm zirconia beads, the mixture was dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then filtered with a 5 μm filter to obtain a PR254 pigment dispersion (P-R1). .

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

(Pigment dispersion (P-R3))
The PR269 pigment dispersion (P--) was prepared in the same manner as the pigment dispersion (P-R1), except that the red refinement-treated pigment (PR-1) was changed to the red refinement-treated pigment (PR-3). R3) was prepared.

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

<Method for producing dye salt forming compound>
(Salt-forming compound (DA-1))
51 parts of vinyl-based resin 1 was added to 2000 parts of water, and after sufficient stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, the reaction solution was dropped onto the filter paper, and it was judged that the salt-forming compound was obtained with the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound (A-1) between acid red 52 and resin 1 having a cationic group in the side chain was obtained. At this time, C.I. in the salt-forming compound (A-1). I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

<Method for producing dye-containing solution>
(Dye-containing solution (DA-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a dye-containing resin solution (DA-1).

Salt-forming compound (A-1): 20.0 parts Propylene glycol monomethyl ether acetate (PGMEA): 80.0 parts

<Structure of nitrogen-containing five-membered ring compound>
Table 2 shows the nitrogen-containing five-membered ring compounds used in the present invention.
The nitrogen-containing five-membered ring compounds (C-1 to 7) were almost colorless compounds and were solid at room temperature (25 ° C.).

[Example 1]
(Coloring composition (R-1))
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-1).

Diketopyrrolopyrrole pigment dispersion 1 (P-R1): 30.0 parts Pigment dispersion or dye-containing solution (P-R2): 10.0 parts Acrylic resin solution (B-1): 19.5 parts included Nitrogen five-membered ring compound (C-1): 0.5 part 1,2-dimethylimidazole polyfunctional monomer (D-1): 3.0 part "Aronix M-402" manufactured by Toagosei Co., Ltd.
Photopolymerization initiator (E-1): 2.0 parts “Irgacure 379” manufactured by BASF
Solvent: 35.0 parts Propylene glycol monomethyl ether acetate (PGMEA)

[Examples 2-14, Comparative Examples 1-9]
(Coloring composition (R-2 to 21)
The pigment dispersion, dye-containing resin solution or dye, acrylic resin solution, nitrogen-containing five-membered ring compound, polyfunctional monomer, photopolymerization initiator, and solvent types and blending amounts (parts by weight) are shown in Tables 3-5. A colored composition (R-2 to 21) was obtained in the same manner as the colored composition (R-1) except that the above was changed.

Abbreviations in Tables 3 to 5 are shown below.
<Multifunctional monomer>
Polyfunctional monomer (D-1): Dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)

<Photopolymerization initiator>
Photopolymerization initiator (E-1): 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (manufactured by BASF “ Irgacure 379 ")

<Solvent>
Solvent: PGMEA (propylene glycol monomethyl ether acetate)

<Evaluation of coloring composition>
The test of the coating film of the obtained coloring composition (R-1-21) was done by the following method. The results of the test are shown in Tables 7 and 8.

<Evaluation of Crystal Precipitation of Red Colored Composition>
Examples 1 to 12 (colored compositions (R-1 to 12) and comparative examples 1 to 9 (colored compositions (R-13 to 21)) were each 100 mm × 100 mm on a 0.7 mm glass substrate. The colored compositions in Examples and Comparative Examples were applied so as to have a film thickness of 2.5 μm, and then exposed to ultraviolet rays through a mask having a predetermined pattern. The resulting 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 measured 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, Δ is a practical level, and × is a level not suitable for practical use.

◎: No precipitation at 250 ° C. ○: Precipitation at 250 ° C.
Δ: Precipitation at 240 ° C ×: Precipitation at 230 ° C or less

<Developability evaluation>
The color filter coloring composition was applied onto a 100 mm × 100 mm, 0.7 mm thick glass substrate using a spin coater to form a 2.5 μm thick coating film. Thereafter, ultraviolet rays were exposed through a photomask having a stripe pattern of 400 μm width, 100 μm width and 50 μm width using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed using a 26 ° C. aqueous sodium carbonate solution, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C. for 20 minutes. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive coloring composition, and this was set as an appropriate development time.

◯ is a very good level, Δ is a practical level, and ■ is a practical level.

○: Development speed is 15 seconds or more and less than 25 seconds Δ: Development speed is 25 seconds or more and less than 30 seconds ×: Development speed is 30 seconds or more

<Pattern shape evaluation>
The cross section of the pattern at the 100 μm photomask portion of the filter segment formed by the above method was evaluated by observation using an electron microscope. It is preferable that the pattern cross section has a forward taper and linearity. The rank of evaluation is as follows.

○: Cross section has forward taper shape and good linearity △: Cross section has forward taper shape, partly poor linearity ×: Cross section has reverse taper shape, and poor linearity

(Dispersion stability evaluation)
About the obtained photosensitive coloring composition, the viscosity after an initial stage and 40 degreeC 4 days was measured, and the viscosity increase degree with respect to an initial stage viscosity was calculated and evaluated. The rank of evaluation is as follows.

○: Viscosity increase rate is 5% or less and good Δ: Viscosity increase rate is greater than 5% and 10% or less ×: Viscosity increase rate is greater than 10%

(Residual film rate evaluation)
In the 400 μm photomask portion of the formed filter segment, the pattern film thickness before and after the heat treatment for 20 minutes in a 230 ° C. oven was measured, and the degree of film thickness change due to heating was calculated and evaluated. The evaluation method and rank are as follows.

Film thickness change before and after heat treatment at 230 ° C = Film thickness after heat treatment at 230 ° C / Film thickness before heat treatment (%)

◯: The rate of change in film thickness is 78% or more and good Δ: The rate of change in film thickness is 76% or more and less than 78% ×: The rate of change in film thickness is less than 76%

From Tables 7 and 8, the coloring composition for a color filter containing the colorant of the present invention and a nitrogen-containing five-membered ring compound showed excellent results in suppressing acicular crystals.
Among these, a nitrogen-containing five-membered ring compound having a molecular weight of 100 to 1,000 and having a straight chain alkyl group or alkylene group having 2 or more and less than 10 carbon atoms directly bonded to at least one nitrogen atom of the five-membered ring portion, It was particularly excellent in suppression of crystal precipitation and brightness, and particularly in developability.

  In addition, from the above results, it is confirmed that the color filter coloring composition containing the colorant and the nitrogen-containing five-membered ring compound can provide an excellent color filter having excellent crystallinity suppression and developability, high brightness, and high brightness. did it.

Claims (5)

A coloring composition containing a colorant (A), a binder resin (B), and a nitrogen-containing five-membered ring compound (C), wherein the colorant (A) contains a diketopyrrolopyrrole pigment. A straight-chain alkyl group or alkylene group having 1 to 20 carbon atoms is directly bonded to at least one nitrogen atom of the five-membered ring portion of the nitrogen-containing five-membered ring compound (C). Coloring composition for color filter.   The coloring composition for a color filter according to claim 1, wherein the nitrogen-containing five-membered ring compound (C) has a molecular weight of 100 to 1,000.   The content of the nitrogen-containing five-membered ring compound (C) is 1 to 20 parts by weight with respect to 100 parts by weight of the diketopyrrolopyrrole pigment contained in the colorant (A). The coloring composition for a color filter according to claim 1 or 2.   Furthermore, a polyfunctional monomer and / or a photoinitiator are contained, The coloring composition for color filters of any one of Claims 1-3 characterized by the above-mentioned.   A color filter comprising a filter segment formed from the colored composition for color filter according to any one of claims 1 to 4 on a substrate.