JP5732924B2 - Pigment dispersion, colored resin composition, color filter, liquid crystal display device and organic EL display - Google Patents

Description

  The present invention relates to a pigment dispersion, a colored resin composition (hereinafter sometimes referred to as “resist”), a color filter, a liquid crystal display device, and an organic EL display. More specifically, a pigment dispersion that can achieve both high contrast, high transmittance (ie, high brightness), and dispersion stability, and has an effect of suppressing generation of crystalline foreign matters after the atomization step and the dispersion step, or after firing. The present invention also relates to a colored resin composition, a color filter having pixels formed using the colored resin composition, a liquid crystal display device having the color filter, and an organic EL display.

Conventionally, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like are known as methods for producing a color filter used for a liquid crystal display device or the like. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.
In recent years, the trend of technological innovation is rapid, and color filters are required to have higher transmittance (hereinafter sometimes referred to as “brightness”), higher contrast, and higher color density. It was. As the color material for determining the color of the color filter, a pigment is generally used from the viewpoint of heat resistance, light resistance and the like. As the pigment, a pigment whose intrinsic absorption spectrum in the visible light wavelength region matches the phosphor emission spectrum of the backlight is preferably used. In order to produce a high-contrast, high-luminance color filter, it is necessary to highly atomize a pigment having a high transmittance, and further to control and disperse the pigment particle size distribution in a small particle size region. The pigment particle size control technology is also rapidly developing.

  For example, as red pigments, dianthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments and the like have been used. In particular, diketopyrrolopyrrole pigments are used in combination with various yellow pigments because of their high permeability, excellent light resistance and heat resistance. However, in recent years, a pigment system with higher permeability has been demanded, and further improvement in permeability by making the primary particle diameter of the pigment finer is being studied.

As a method of atomizing the pigment, for example, the pigment, the water-soluble inorganic salt such as salt and the water-soluble organic solvent are mechanically kneaded together with a kneader or the like, and then the inorganic salt and the organic solvent are removed by washing with water. There are known methods such as a salt milling method for obtaining a pigment that has been converted into a pigment.
However, pigments generally have high orientation and are easily crystallized by reorientation with external energy. Therefore, the more energy is applied for the purpose of reducing the particle size in the atomization step, the more easily the crystal transition of the pigment occurs due to energy such as grinding and heat. Further, similar crystal transition easily occurs in firing in the color filter manufacturing process.

In addition, the pigment particle size is reduced, the surface area of the pigment is increased, and the amount of dispersant adsorbed is insufficient in the pigment dispersion step, causing reaggregation, and the dispersion system is likely to become unstable. Accordingly, in recent years, it has become a very important technical issue how to make a pigment finely divided to increase brightness and contrast exist as a stable dispersion.
In order to solve such problems, for example, in Patent Documents 1, 2, and 3, when preparing a pigment dispersion, a diketopyrrolopyrrole pigment derivative in which a sulfo group or a salt thereof is introduced into a diketopyrrolopyrrole pigment. In the examples, C.I. I. Pigment Red 254 (hereinafter sometimes referred to as “PR254”) is a C.I. I. Pigment Red 254 is used in combination.

Patent Document 4 describes a composition containing a sulfonated diketopyrrolopyrrole and a Mannich type-substituted dihydroquinaclone. In the examples, phthalimido-methyl 6,13-dihydroquinacridone and diketopyrrolopyrrole are described. An example using sodium sulfonate and PR254 is given.
The pigment derivative has an advantage that it has a high affinity with the pigment and is easily adsorbed on the pigment surface because the pigment is applied to the mother skeleton. When such a pigment derivative is added at the time of atomization and dispersion, it can be easily adsorbed to the pigment, and high orientation derived from the pigment is inhibited by the steric repulsion of the sulfo group and its salt introduced into the pigment derivative. It is considered that the crystal growth of the pigment can be suppressed. Further, the pigment derivative has a certain effect in improving dispersion stability due to electrostatic repulsion of the introduced sulfo group or a salt thereof and interaction with the dispersant.

JP 2000-160084 A JP 2006-265528 A JP 2007-23266 A JP-T-2004-505157

  However, according to the verification by the present inventors, a highly atomized pigment, for example, a highly atomized diketopyrrolopyrrole pigment is sufficiently dispersed and dispersed even by using the various methods described above. It was insufficient to maintain high stability and to obtain high contrast and high brightness. This is because the pigment derivative itself mixed for the purpose of suppressing the crystal transition is also highly oriented, and the crystal transition is not sufficiently suppressed. Moreover, by mixing a pigment derivative having a pigment as a mother skeleton, the transparency of the pigment itself is often impaired, and a pigment dispersion containing a pigment derivative having a pigment as a mother skeleton and a colored resin composition for a color filter are Not necessarily satisfy current market requirements. Therefore, the development of a new material that adsorbs efficiently to the pigment, has a low orientation of the compound itself, and can sufficiently suppress the crystal transition of the pigment by inhibiting the re-orientation of the pigment, while not impairing the permeability of the pigment. It is desired.

The present invention has been made in view of the above problems, and its object is as follows.
(1) A highly finely divided pigment in recent years can be efficiently and stably dispersed with a small amount of addition without lowering the brightness of the pigment itself, and as a result, a color filter with high brightness, high contrast and high color density. A pigment dispersion and a colored resin composition capable of producing
(2) To provide a color filter with high brightness, high contrast, high color density and high quality using the above colored resin composition.

  (3) To provide a high-quality liquid crystal display device and organic EL display using the color filter.

  As a result of diligent studies to solve the above problems, the present inventors have mixed an alkaline earth metal salt of a water-soluble dye having an acidic group with a pigment without reducing the brightness of the pigment itself. Even with finely divided pigments, it is possible to disperse efficiently and stably with a small amount of addition, providing a color filter that exhibits sufficiently high brightness, contrast, and color density for liquid crystal display devices or organic EL displays. As a result, the present invention has been completed.

The gist of the present invention is as follows.
(1) (A) a pigment, and (B) an alkaline earth metal salt of a water-soluble dye having an acidic group ,
The (B) alkaline earth metal salt of a water-soluble dye having an acidic group contains a compound represented by the following general formula (1) or a compound represented by the general formula (2) Dispersion.

(R ¹¹ and R ¹² in the general formula (1) are each independently an aromatic group which may have a substituent, or a structure represented by the following general formula (3) or the general formula (4). The structure represented by is shown.
R ²¹ in the general formula (2) represents a 5- or 6-membered heterocyclic group containing one or more nitrogen atoms.
R ²² in the general formula (2) is an aromatic group which may have a substituent, a structure represented by the following general formula (3), a structure represented by the following general formula (4), or the following general formula The structure represented by Formula (5) is shown. n represents 0 or 1.

(In the above general formulas (3) and (4), R ¹ , R ² , R ³ and R ⁴ each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Represents an optionally substituted alkoxy group or an optionally substituted aromatic group, and * represents a site bonded to the azo group in the general formula (1) or (2).
R ⁵ in the general formula (5) has the same meaning as R ¹ and R ^{2 in} the general formula (3) and R ³ and R ⁴ in the general formula (4). * Shows the site | part couple | bonded with the azo group in General formula (2). )
X in the general formula (1) represents a direct bond or any linking group represented by the following structural formulas (1-1) to (1-11).

(Note that * in the above structural formulas (1-1) to (1-11) represents a site bonded to the benzene ring in the general formula (1).
R ¹¹¹ in Structural Formula (1-3) is a hydrogen atom, a hydroxyl group, or —NA ¹ A ² (A ¹ and A ² are each independently a hydrogen atom or an alkyl group optionally having a substituent. Represents an alkoxy group which may have a substituent, or an aromatic group which may have a substituent. )
Z in the general formula (2) is a direct bond or any structure represented by the following structural formulas (2-11) to (2-13) (note that the following structural formula (2-11) ) To (2-13) indicate a site bonded to the benzene ring and R ²² in the general formula (2).

In addition , the benzene ring in the general formulas (1) and (2) further includes a nitro group, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a sulfo group. At least one substituent selected from the group consisting of a sulfonate group, a carboxy group, a carboxylate group, a phospho group, a phosphate group, and an optionally substituted aromatic group You may have.

Further, R ²² in R ¹¹ and R ¹² in the general formula (1), the general formula (2), R ¹¹¹ in structural formula (1-3) and the general formula (1), Moshiku during (2) At least one of the substituents bonded to the benzene ring is an acidic alkaline earth metal salt group or a group having an acidic alkaline earth metal salt group. )
(2) (A) The pigment is C.I. I. (Color Index) selected from the group consisting of Pigment Red 177, Pigment Red 242, Pigment Red 254, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 150, Pigment Yellow 180, Pigment Green 7, Pigment Green 36, and Pigment Green 58 The pigment dispersion according to (1), further comprising at least one pigment.
(3) The content of the alkaline earth metal salt of the water-soluble dye having an acidic group (B) is 0.01 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the pigment (A). The pigment dispersion according to (1) or (2) above.
(4) The pigment dispersion according to any one of (1) to (3), further comprising (C) a dispersant.
(5) A colored resin composition for a color filter, comprising the pigment dispersion according to any one of (1) to (4), and (D) a binder resin.
(6) The colored resin composition for color filters as described in (5) above, further comprising (E) a polymerizable monomer.
(7) The colored resin composition for color filters as described in (5) or (6) above, further comprising (F) a photopolymerization initiator and / or a thermal polymerization initiator.
(8) A color filter comprising a pixel produced using the colored resin composition for a color filter according to any one of (5) to (7).
(9) A liquid crystal display device comprising the color filter according to (8).
(10) An organic EL display comprising the color filter according to (8).

In the pigment dispersion and the colored resin composition of the present invention, an alkaline earth metal salt of a water-soluble dye having an acidic group is added in the pigment atomization step and the dispersion step, and in these steps and the color filter firing step. The crystal transition of the pigment can be sufficiently suppressed, and the pigment can be efficiently dispersed with a small addition amount without lowering the luminance (transmittance) of the pigment itself. Further, by using the pigment dispersion and the colored resin composition, a color filter with high luminance, high contrast and high color density can be produced, and as a result, a high-quality liquid crystal display device and an organic EL display are provided. be able to.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present invention. It is a typical figure for demonstrating the method to measure the chromaticity of the parallel transmission light and orthogonal transmission light of a colored board in an Example. It is a figure showing the emission spectrum of the backlight 37 used in the Example. It is a figure which shows the spectral characteristics of the polarizing plates 33 and 35 used in the Example.

The constituent requirements and embodiments of the present invention will be described in detail below, but these are examples of the embodiments of the present invention, and the present invention is not limited to these contents.
“(Meth) acryl” and the like mean “at least one of acryl and methacryl” and “(meth) acrylate” and the like mean “at least one of acrylate and methacrylate”. “Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

Further, “total solid content” means all components other than the solvent components described later, which are contained in the pigment dispersion or the colored resin composition.
In the present invention, unless otherwise specified, the weight average molecular weight (Mw) refers to a weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography). “C.I.” means a color index (C.I.).

Furthermore, in the present invention, the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base and the equivalent weight of KOH per 1 g of the solid content of the dispersant. is there. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
<Constituent components of pigment dispersion>
Below, each component of the pigment dispersion liquid of this invention is demonstrated. The pigment dispersion of the present invention comprises (A) a pigment and (B) an alkaline earth metal salt of a water-soluble dye having an acidic group as essential components, and if necessary, other additives and solvents other than these components. Etc. may be blended.

Hereinafter, each component will be described.
<(A) Pigment>
The pigment dispersion of the present invention comprises (A) a pigment as an essential component, and from the viewpoint of the effects of the invention, the (A) pigment is usually a red pigment, blue pigment, green pigment, yellow pigment, purple pigment, orange pigment. Various color pigments such as brown pigments can be used.

Examples of chemical structures of various pigments include organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition to these, various inorganic pigments can also be used.
Specific examples of pigments that can be used in the present invention are shown below by pigment numbers, but are not limited to these examples.

First, as a red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8,
9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 19 , 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273 274, 275, 276 and the like. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 209, 224, 242, 254, and the like.

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

Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, and the like. Of these, C.I. I. Pigment green 7, 36, 58, and the like.
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 pigments described in JP-A-2005-325350 and JP-A-2007-25687. Of these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and the pigments described in the above-mentioned 2 publications, and more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180, and the pigments described in the above-mentioned 2 publications.

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. Of these, C.I. I. Pigment violet 19, 23, etc., more preferably C.I. I. Pigment violet 23 and the like.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Of these, C.I. I. Pigment orange 38, 71 and the like.

Alternatively, the pigment dispersion of the present invention may be used to prepare a colored resin composition as will be described later to form a resin black matrix of a color filter. In that case, a black pigment can be used. . In addition, a black pigment may be used independently and may mix and use pigments, such as red, green, and blue. Further, it may be an inorganic pigment or an organic pigment.
The (A) pigment used in the present invention is a red or yellow pigment from the viewpoint of the color of the pigment dispersion when used in combination with an alkaline earth metal salt of a water-soluble dye having an acidic group (B) described later. Diketopyrrolopyrrole pigments and anthraquinone pigments that are mainly pigmented by hydrogen bonds are preferred. As the diketopyrrolopyrrole pigment, for example, Pigment Red 254, Pigment Red 255, Pigment Red 264, and Pigment Red 272 are preferable.
On the other hand, since the compound represented by the general formula (1) has very high planarity, intermolecular π-π interaction is also possible. Accordingly, pigments formed by intermolecular π-π interaction, that is, Pigment Red 242, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 150, Pigment Yellow 180, Pigment Green 7 and Pigment Green 36 are preferable.
Among these, in particular, C.I. I. Pigment Red 254 and Pigment Yellow 138 are most preferable.

Examples of inorganic pigments that can be used in the present invention include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide.
In addition, the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, as the (A) pigment, a red pigment and a yellow pigment can be used in combination, or a green pigment and a yellow pigment can be used in combination.

The average primary particle size of the pigment (A) according to the present invention is usually 100 nm or less, preferably 80 nm or less, more preferably 20 nm or more and 70 nm or less. Since the present invention is particularly effective in the case of a composition containing a highly atomized pigment, the case of containing a pigment having an average primary particle size of 20 nm to 60 nm is particularly preferable.
By making the average primary particle size of the pigment (A) used within the above range, the depolarization characteristics are kept good, high contrast and transmittance are realized, dispersion stability is good, heat resistance and light resistance A color filter pixel forming composition having excellent properties can be obtained.

The primary particle diameter of the pigment can be determined by the following method.
First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). However, in the case of organic pigments, the particle diameter of each pigment particle is the diameter corresponding to the area circle converted to the diameter of a circle having the same area, and the particle diameter of each of plural (usually about 200 to 300) pigment particles. Ask for. Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.

The pigment (A) thus obtained may be used alone, but may be used alone or in combination of two or more types within a range not impairing the effects of the present invention.
The content of the pigment (A) in the present invention is usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, and usually 0.1% by weight or more with respect to the total solid content. , Preferably 0.5% by weight or more, more preferably 1% by weight or more.

(A) By setting the pigment content within the above range, the film thickness with respect to the color density does not become too large, and there is no adverse effect on the gap control during the formation of a liquid crystal cell, and sufficient image formability is obtained. In addition, the dispersed state of the pigment is maintained, and aggregation and sedimentation are unlikely to occur. As a result, problems such as thickening and lowering of brightness and contrast can be solved.
<(B) Alkaline earth metal salt of water-soluble dye having acidic group>
The pigment dispersion of the present invention is an alkaline earth metal salt of the water-soluble dye having an acidic group (B) described below and (B) an acidic group (hereinafter sometimes referred to as “component (B)”). It is characterized by containing.

The acidic group is a group that releases protons when dissolved in water, and usually includes a sulfo group, a carboxy group, and a phospho group.
The water-soluble dye is a compound that has any one of a hydroxyl group, an acidic group, and a basic group to promote dissolution in water, and has an absorption spectrum in the visible light wavelength region. In addition, the water-soluble dye in (B) component of this invention has an acidic group. Many of these are recorded in the color index. For example, 2,2 ′-(1,2-ethenediyl) bis [5-[(4-hydroxyphenyl) azo] benzenesulfonic acid] disodium, 2- [4-[[6-[[[[4- (acetyl Amino) phenyl] amino] carbonyl] amino] -1-hydroxy-3-sulfo-2-naphthyl] azo] -3-sulfophenyl] -6-methyl-7-benzothiazolesulfonic acid trisodium, 4-[[7 -[(2,4-diaminophenyl) azo] -1-hydroxy-3-sulfonaphthalen-2-yl] azo] -4 '-[(4-hydroxyphenyl) azo] [1,1'-biphenyl]- Examples thereof include compounds such as compounds such as trisodium 2,2′-disulfonate.
The alkaline earth metal is selected from the long-period periodic table (hereinafter, unless otherwise specified, the term “periodic table” refers to the long-period periodic table). Says metal.

  Since the component (B) used in the present invention has an alkaline earth metal salt group of an acidic group, it is hardly soluble in water, and does not flow into a solvent such as water in the atomization step. ) The pigment can be sufficiently dispersed and high dispersion stability can be secured. In addition, component (B) contains at least one of a monoazo compound, a bisazo compound, and a diazoamino compound. High transmittance can be achieved without impairing the properties.

The component (B) used in the present invention can be used without particular limitation as long as it is an alkaline earth metal salt of a water-soluble dye having an acidic group, but also contains the component (B) as described above. It is preferable to use a monoazo compound, a bisazo compound, or a diazoamino compound from the viewpoint of preventing a decrease in the transmittance of the composition.
Examples of the monoazo compound include 2 ′, 2 ′ ″-[azobis (4,1-phenylene)] bis (6-methyl-2,6′-bibenzothiazole-7-calcium sulfonate), 3,3. '-[[1,1'-biphenyl] -4,4'-diylbis (azo)] bis [6-hydroxybenzoic acid calcium], 6-methyl-2'-[4- [2-oxo-1- ( Phenylaminocarbonyl) propylazo] phenyl] -2,6′-bibenzothiazole-7-sulfonic acid magnesium, 5-[[4-[[6-[(4-aminobenzoyl) amino] -1-hydroxy-3- Sulfo-2-naphthalenyl] azo] benzoyl] amino] -2-hydroxybenzoate, 2- [4-[[6-[[[[4- (acetylamino) phenyl] amino] carbonyl] amino] -1- Hide Roxy-3-sulfo-2-naphthyl] azo] -3-sulfophenyl] -6-methyl-7-benzothiazolesulfonate) -ethoxy-4-hydroxy-3-[[4- (6-methylbenzothiazole 2-yl) phenyl] azo] -2,7-naphthalenedisulfonic acid calcium and the like.

  Examples of the bisazo compound include 2,2 ′-(1,2-ethenediyl) bis [5-[(4-hydroxyphenyl) azo] benzenesulfonic acid magnesium], 3,3 ′-[carbonylbis [imino (2 -Methyl-4,1-phenylene) azo]] bis [1,5-naphthalenedisulfonate], 3,5-bis [(2,4-diamino-5-nitrophenyl) azo] -4-methylbenzenesulfone Acid calcium, 3,3 ′-[(1,6-dihydro-6-oxo-1,3,5-triazine-2,4-diyl) bis [imino (5-methoxy-2-methyl-4,1- Phenylene) azo]] bis (barium 1,5-naphthalenedisulfonate), 7-[[4-[[[2-methoxy-4-[(3-sulfophenyl) azo] phenyl] aminocarbonyl] Mino] phenyl] azo] -1,3-naphthalenedisulfonate, 3,3 ′-[[6-[(2-hydroxyethyl) amino] -1,3,5-triazine-2,4-diyl] bis [Imino (2-methyl-4,1-phenylene) azo]] bis [1,5-naphthalenedisulfonate], 7- (benzoylamino) -4-hydroxy-3-[[4-[(4-so Dioxysulfonylphenyl) azo] phenyl] azo] -2-naphthalenesulfonic acid barium), 6-hydroxy-2- [3-[(2-hydroxy-6-sulfo-1-naphthyl) azo] phenyl] -7- (Phenylazo) -1H-naphtho [1,2-d] imidazole-8-sulfonate calcium and the like.

  Further, as the diazoamino compound, for example, 2- [4- [1- (4-nitrophenyl) triaze-3-yl] phenyl] -6-methylbenzothiazole-7-sulfonate calcium, 2-hydroxy-5- [ [4 ′-[3- [4- (6-Methyl-7-sodiosulfobenzothiazol-2-yl) phenyl] triazen-1-yl] -1,1′-biphenyl-4-yl] azo] benzoic acid Acid calcium, 2-hydroxy-5-[[4 ′-[3- (4-sodiosulfophenyl) triaze-1-yl] -1,1′-biphenyl-4-yl] azo] calcium benzoate, 4 , 4 ′-(triazene-1,3-diyl) bis (calcium benzoate) and the like can be used.

These azo compounds may be used alone or in combination of two or more. [Compound represented by general formula (1)]
As the component (B) used in the present invention, a compound represented by the following general formula (1) is preferably used from the viewpoint of the strength of adsorption to the pigment by π-π interaction.

In the general formula (1), R ¹¹ and R ¹² are each independently an aromatic group which may have a substituent, a structure represented by the following general formula (3), or the following general formula (4). ). When R ¹¹ and / or R ¹² is an aromatic group, examples of these aromatic groups include a phenyl group, a naphthyl group, a biphenyl group, and a fluorenyl group. Further, these aromatic groups are substituted with, for example, the same group as the substituent of the aromatic when any of R ¹ , R ² , R ³ and R ⁴ described later is an aromatic group. It may be.

However, from the adsorption performance on the pigment surface by intermolecular hydrogen bonding with the (A) pigment of the component (B), R ¹¹ and R ¹² in the above general formula (1) are each independently the following general formula (3) Or a structure represented by the general formula (4). Furthermore, since there are many locations where hydrogen bonds are formed, a structure represented by the following general formula (3) is particularly preferable.

In the above general formulas (3) and (4), R ¹ , R ² , R ³ and R ⁴ each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Represents an alkoxy group which may be substituted, or an aromatic group which may have a substituent, and * represents a site bonded to the azo group in the general formulas (1) and (2).
As the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecanyl group, A linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, such as a dodecanyl group, can be exemplified. More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or a t-butyl group.

  Examples of alkoxy groups include methoxy, ethoxy, propoxy, methoxypropyl, ethoxymethyl, butyl, methoxypropyl, ethoxyethyl, propoxymethyl, pentyl, methoxybutyl, ethoxybutyl, and propoxy. A linear, branched, or cyclic alkoxy group having 1 to 20 carbon atoms, such as an ethyl group, a t-butoxymethyl group, a pentoxy group, a methoxybutyl group, an ethoxypropyl group, a propenylethyl group, an isoproponylethyl group, and a hexyl group. Can be mentioned. More preferred are linear or branched alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group, methoxypropyl group, ethoxymethyl group, butyl group, methoxypropyl group, ethoxyethyl group and the like.

Examples of the aromatic group include a phenyl group, a naphthyl group, a biphenyl group, and a fluorenyl group, and a phenyl group is more preferable.
When any of R ¹ , R ² , R ³ and R ⁴ is the alkyl group or alkoxy group, the alkyl group may further have an arbitrary substituent. Examples of the optional substituent that the alkyl group or alkoxy group may further have include a hydroxyl group, an amino group, a carboxy group, a sulfo group, a sulfonate group, a carboxylate group, a phospho group, and a phosphorus group. Acid group or the like is preferred.

When any of R ¹ , R ² , R ³ and R ⁴ is the aromatic group, the aromatic group may further have an arbitrary substituent. Examples of the optional substituent that the aromatic group may further include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl Group, octyl group, nonyl group, decanyl group, undecanyl group, dodecanyl group, etc., linear or branched alkyl group having 1 to 20 carbon atoms; phenyl group, halogenated phenyl group, alkylphenyl group, alkylhalogenated phenyl group, alkoxy Aryl groups such as phenyl group, alkoxycarbonylphenyl group, naphthyl group; methoxy group, ethoxy group, propoxy group, methoxypropyl group, ethoxymethyl group, butyl group, methoxypropyl group, ethoxyethyl group, propoxymethyl group, pentyl group, Methoxybutyl group, ethoxybutyl group, propoxyethylene A straight chain or branched alkoxy group having 1 to 20 carbon atoms such as a group, t-butoxymethyl group, pentoxy group, methoxybutyl group, ethoxypropyl group, proponylethyl group, isoproponylethyl group; nitro group; hydroxyl group; carboxy A group; a sulfo group; a sulfonate group; a carboxylate group; a phospho group; a phosphate group, or a combination of these substituents.

R ¹ , R ² , R ³ and R ⁴ are methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, phenyl group, 4-chlorophenyl group, 4-ethoxyphenyl group. 2-chloro-4-methylphenyl group and the like are more preferable.
X in the general formula (1) represents a direct bond or any linking group represented by the following structural formulas (1-1) to (1-11).

In addition, * in the said structural formula (1-1)-(1-11) shows the site | part couple | bonded with the benzene ring in General formula (1).
R ¹¹¹ in Structural Formula (1-3) is represented by a hydroxyl group or —NA ¹ A ² (A ¹ and A ² have the same meanings as R ¹ , R ² , R ³ and R ⁴ ). Represents a group. R ¹¹¹ is more preferably a dimethylamino group, a diethylamino group, a dibutylamino group, a phenylamino group, or the like. In addition, you may have arbitrary substituents about the phenyl site | part in a phenylamino group.

X in the general formula (1) is either a direct bond, a linking group represented by the structural formula (1-1), or a linking group represented by the structural formula (1-2). Is preferred. A direct bond or a linking group represented by the structural formula (1-1) is particularly preferable.
When the compound represented by the general formula (1) is used as the component (B) used in the present invention, the benzene ring in the general formula (1) further has a nitro group, a hydroxyl group, and a substituent. May have an alkyl group, an alkoxy group which may have a substituent, a sulfo group, a sulfonate group, a carboxy group, a carboxylate group, a phospho group, a phosphate group, and a substituent. It may have at least one substituent selected from the group consisting of aromatic groups. Examples of the alkyl group, alkoxy group, and aromatic group include the same groups as those described above for R ^{1 to} R ⁴ .

In view of the effect of the present invention, the benzene ring in the general formula (1) preferably further has a substituent such as a sulfo group, a sulfonate group, a carboxy group, or a carboxylate group.
In the present invention, when the compound represented by the general formula (1) is used as the component (B), R ¹¹ and R ¹² in the general formula (1), and in the general formulas (3) and (4) Among the R ¹ , R ² , R ³ , R ⁴ , R ¹¹¹ in the structural formula (1-3), and the substituent bonded to the benzene ring in the general formula (1), at least one is an alkaline earth having an acidic group It is a group of a metal salt or a group having an alkaline earth metal salt group of an acidic group.

In the compound represented by the general formula (1), the number of acidic alkaline earth metal salt groups is usually 1 to 6. If the number of the alkaline earth metal salt group of the acidic group is too large, the elution of ions increases, and the electrical characteristics may be deteriorated. The number of the alkaline earth metal salt group of the acidic group is more preferably 1 to 4, and still more preferably 1 to 2.
Examples of the alkaline earth metal salt group of acidic group include, for example, calcium sulfonate, magnesium sulfonate, barium sulfonate, calcium phosphate, barium phosphate, calcium carboxylate and the like, more preferably, calcium sulfonate, Or it is calcium carboxylate.

  When the compound represented by the above general formula (1) is used as the component (B) used in the present invention, in addition to hydrogen bonding, π-π stacking with the pigment due to an increase in planarity is possible, and the pigment and A compound represented by the following general formula (1 ′) is preferable in that it is strongly adsorbed.

However, X, R ¹¹ and R ¹² in the general formula (1 ′) have the same meaning as in the general formula (1). Further, the benzene ring in the general formula (1 ′) may further have an arbitrary substituent, and specifically, for example, as an arbitrary substituent in the benzene ring in the general formula (1). Examples thereof include the same group as the group.
Although the specific example of the compound represented by the said General formula (1) used as (B) component of this invention is illustrated below, it is not necessarily limited to these.

Among the structural formulas, the compound represented by the structural formula (1-102) and the structural formula (1-103) are more preferable from the viewpoint of efficiently suppressing dispersion stability and pigment crystal transition. A compound represented by the structural formula (1-104), a compound represented by the structural formula (1-105), a compound represented by the structural formula (1-106), and a structural formula (1-107). A compound represented by the structural formula (1-108), a compound represented by the structural formula (1-109), a compound represented by the structural formula (1-114), a structural formula (1- 116), a compound represented by structural formula (1-133), a compound represented by structural formula (1-135), a compound represented by structural formula (1-141), a structural formula ( 1-156), compound represented by Structural Formula (1-188), structure (1-199) a compound represented by a compound represented by the compounds represented by structure (1-203), and the structural formula (1-214).
[Compound represented by formula (2)]

  In addition, the use of a compound represented by the following general formula (2) as the component (B) used in the present invention also facilitates strong adsorption on the pigment surface due to high flatness, resulting in high dispersion stability. It is preferable in that it has.

In the general formula (2), R ²² represents an aromatic group which may have a substituent, a structure represented by the general formula (3), a structure represented by the general formula (4), or The structure represented by the following general formula (5) is shown. In addition, when R < ²² > is a structure represented by the said General formula (3) or (4), * in these general formula represents the site | part couple | bonded with the azo group in General formula (2). n represents 0 or 1.

When R ²² in the general formula (2) is an aromatic group that may have a substituent, the type of the aromatic and the type of the substituent that the aromatic has are, for example, the general formula ( it may be the same as those exemplified as ^{R 11} and ^{R 12} in 1).
However, considering the adsorption performance on the pigment surface by intermolecular hydrogen bonding with the component (B) of the component (B), R ²² is a structure represented by the general formula (3), the general formula (4 ) Or a structure represented by the following general formula (5). More preferably, it is a structure represented by the general formula (3) or a structure represented by the following general formula (5).

(However, R ⁵ in the general formula (5) has the same meaning as R ¹ and R ^{2 in} the general formula (3) and R ³ and R ⁴ in the general formula (4). (The site | part couple | bonded with the azo group in Formula (2) is shown.)
Z in the general formula (2) is a direct bond or any structure represented by the following structural formulas (2-11) to (2-13) (note that the following structural formula (2-11) ~ * in (2-13) indicates a site binding to the general formula (2) a benzene ring and ^{R 21} in.). Z is preferably a direct bond from the viewpoint of improving the adsorption performance to the pigment by the π-π interaction.

In said formula (2-13), the benzene ring and the benzothiazole ring may have a substituent other than a connection part.
R ²¹ in the general formula (2) represents a 5- or 6-membered heterocyclic group containing one or more nitrogen atoms. More specifically, for example, the following structural formulas (2-21) to (2) A heterocyclic group represented by -33). More preferred is a benzothiazolyl group or a pyrimidyl group.

When the compound represented by the general formula (2) is used as the component (B) of the present invention, the benzene ring in the general formula (2) is further substituted with a nitro group, a hydroxyl group, and a substituent as in the general formula (1). An alkyl group which may have a group, an alkoxy group which may have a substituent, a sulfo group, a sulfonate group, a carboxy group, a carboxylate group, a phospho group, a phosphate group, and You may have at least 1 group selected from the group which consists of the aromatic group which may have a substituent. Specific examples of the alkyl group, alkoxy group, and aromatic group include the same groups as those described above for R ^{1 to} R ⁵ .

In addition, from the point that the effect of the present invention can be obtained satisfactorily, the benzene ring in the general formula (2) is further a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group or an ethyl group; It preferably has a substituent such as an ethoxy group or the like having a straight or branched alkoxy group having 1 to 3 carbon atoms; sulfo; a sulfonate group; a carboxy group; a carboxylate group.
In the present invention, when the compound represented by the general formula (2) is used as the component (B), R ²² in the general formula (2), R ¹ in the general formulas (3) to (5), R ² , R ³ , R ⁴ , R ⁵ , and among the substituents bonded to the benzene ring in the general formula (2), at least one is an alkaline earth metal salt group of an acidic group, or an acidic group This is a group having an alkaline earth metal salt group.

In the compound represented by the general formula (2), the number of the alkaline earth metal salt group of the acidic group is usually 1 to 6, more preferably 1 to 3, and further preferably 1 to 2. It is.
Examples of the group of the alkaline earth metal salt of an acidic group include the same groups as in the general formula (1).
Although the specific example of the compound represented by the said General formula (2) used as (B) component of this invention is illustrated below, it is not necessarily limited to these. From the viewpoint of efficiently suppressing dispersion stability and crystal transition of the pigment, the compound represented by the following structural formula (2-101), the compound represented by the structural formula (2-104), and the structure are more preferable. Compound represented by formula (2-105), compound represented by structural formula (2-108), compound represented by structural formula (2-112), compound represented by structural formula (2-115) , A compound represented by the structural formula (2-117), a compound represented by the structural formula (2-149), a compound represented by the structural formula (2-150), and a structural formula (2-159). And a compound represented by the structural formula (2-160).

In the present invention, as the component (B), the compound represented by the general formula (1) or the compound represented by the general formula (2) may be used alone or in combination of two or more. May be.
The content of component (B) is usually 0.01 parts by weight or more, 1 part by weight or more, and usually 90 parts by weight or less, preferably 60 parts by weight or less, based on 100 parts by weight of (A) pigment. The amount is preferably 40 parts by weight or less.
If it is within the above range, it is difficult to elute ions, so that the influence on electric characteristics is small, and it is preferable in that sufficient effects can be obtained for dispersion stability and pigment crystal transition.

<(C) Dispersant>
The pigment dispersion of the present invention contains (C) a dispersant.
The dispersant (C) is preferably an alkaline earth metal salt of the water-soluble dye having an acidic group (B) of the present invention, but may contain other dispersant.
Other dispersants are not particularly limited as long as the effects of the present invention are not impaired. From the viewpoint of dispersion stability, (C-1) a graft copolymer containing a nitrogen atom (hereinafter referred to as (C-1) And / or (C-2) an acrylic block copolymer containing a nitrogen atom (hereinafter also referred to as (C-2) a dispersant). Is preferred. More preferred is (C-2) a dispersant.

  In any of these (C-1) and (C-2) dispersants, the nitrogen atom contained in the dispersant structure has an affinity for the pigment surface, and the portion other than the nitrogen atom has an affinity for the medium. By increasing it, it is estimated that it contributes to the improvement of dispersion stability as a whole. In addition, the performance of (C) the dispersant is greatly influenced by the adsorption behavior to the solid surface. Regarding the relationship between the molecular architecture and the adsorption behavior, it is known that when the same unit is used, the adsorption behavior is excellent in the order of random copolymerization <graft copolymer <block copolymer (for example, Jones and Richards, “Polymers at Surfaces and Interfaces” p. 281).

<(C-1) Graft copolymer containing nitrogen atom>
(C-1) The graft copolymer containing a nitrogen atom is preferable in that (C) the pigment can be dispersed very efficiently. The reason for this is not clear, but it has a structure that can positively eliminate the part (molecule) that hinders the adsorption of the pigment and the dispersing agent around the adsorption part to the pigment. This is probably because of this. As the graft copolymer containing a nitrogen atom, those having a repeating unit containing a nitrogen atom in the main chain are preferred. Especially, it is preferable to have a repeating unit represented by the following general formula (I) and / or a repeating unit represented by the following general formula (II).

(In the general formula (I), R ⁵¹ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any one of the following general formulas (III) to (V).)
In the general formula (I), R ⁵¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, more preferably ethylene. It is a group. A represents a hydrogen atom or any one of the following general formulas (III) to (V), preferably the following general formula (III).

(In the general formula ^{(II), R 51,} A is the same meaning as ^{R 51,} A of the general formula (I).)

(In General Formula (III), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, and hexylene is preferable. Represents an integer of 1 to 20, preferably an integer of 5 to 10.)

(In General Formula (IV), M ₁ represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene, or an alkyleneoxy having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy. W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, butylene, etc. Among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable. ₂ represents a hydrogen atom or —CO—R ⁵² (R ⁵² represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc .; 5 is preferable.) Q represents an integer of 1 to 20, and preferably an integer of 5 to 10.)

(In the above general formula (V), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, among which stearyl and other carbon atoms having 10 to 20 carbon atoms. A C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as an alkyl group and monohydroxystearyl is preferred.)
(C-1) The content of the repeating unit represented by formula (I) or (II) in the dispersant is preferably higher, and is generally 50 mol% or more in total, preferably 70 mol% or more. is there. The repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) may be both present, and the content ratio is not particularly limited, but the general formula (I) It is preferable to contain a large number of repeating units. The total number of repeating units represented by the general formula (I) or (II) is usually 1 to 100, preferably 10 to 70, more preferably 20 to 50 in one molecule.

The (C-1) dispersant may contain a repeating unit other than the general formulas (I) and (II). Examples of the other repeating unit include an alkylene group and an alkyleneoxy group. In addition, the graft copolymer preferably has a terminal of —NH ₂ and —R ⁵¹ —NH ₂ (R ⁵¹ is synonymous with R ^{51 of} formula (I)).
In addition, as long as the (C-1) dispersant is a graft copolymer, the main chain may be linear or branched.

(C-1) The amine value of the dispersant is usually 5 to 100 mgKOH / g, preferably 10 to 70 mgKOH / g, and more preferably 15 to 40 mgKOH / g or less.
If the amine value is too low, the dispersion stability may be lowered and the viscosity may become unstable. On the other hand, if the amine value is too high, the residue may increase or the electrical characteristics after the liquid crystal panel is formed may be reduced. There is a possibility.

The amine value (in terms of effective solid content) of the dispersant is represented by the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
(W: represents the amount of the dispersant sample weighed [g], V: represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)
Moreover, although the acid value of (C-1) a dispersing agent is based also on the presence and kind of the acidic group which becomes the origin of the said acid value, generally the one where a lower one is preferable.

(C-1) The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) of the dispersant is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. If the weight average molecular weight (Mw) is less than 3000, the aggregation of the pigment cannot be prevented and the viscosity or gelation may occur. Conversely, if the weight average molecular weight (Mw) exceeds 100000, the viscosity itself becomes high. The solubility in organic solvents may be insufficient. Further, the developability and resolution may be lowered.

As a method for synthesizing the (C-1) dispersant, for example, the method described in JP-B-63-30057 can be used.
Further, as the (C-1) dispersant, a commercially available graft copolymer having the same structure as that described above can be used.
<(C-2) Acrylic Block Copolymer>
(C-2) An acrylic block copolymer is preferable in that (A) the pigment can be dispersed very efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that obstruct the dispersing agent when adsorbed on the pigment.

The acrylic block copolymer is particularly preferably a block copolymer comprising an A block having a solvophilic group and a B block having a nitrogen atom-containing functional group.
Specific examples of the B block having a nitrogen atom-containing functional group include a unit structure having a quaternary ammonium base and / or an amino group in the side chain, while quaternary ammonium is used as a solvophilic A lock. Examples include a unit structure having no base and amino group.

The B block constituting the acrylic block copolymer has a unit structure having a quaternary ammonium base and / or an amino group, and has a pigment adsorption function.
Further, when the B block has a quaternary ammonium base, the quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group. Good. Moreover, as such a quaternary ammonium base, what contains the partial structure represented with the following general formula (VI) especially is preferable.

In the above general formula (VI), R ³⁴ represents a hydrogen atom or a methyl group. X ¹ represents a divalent linking group. R ³¹ , R ³² and R ³³ are each independently an alkyl group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 15 carbon atoms, or optionally substituted. Aralkyl groups having 7 to 20 carbon atoms are preferred.

Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, methyl, ethyl, propyl, butyl, benzyl and the like are preferable.
In the general formula (VI), examples of the divalent linking group X ¹ include an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ³⁵ —, —COO—R ³⁶ — (provided that
R ³⁵ and R ³⁶ are each independently a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ³⁷ —O—R ³⁸ —: R ³⁷ and R ³⁸ are Each independently represents an alkylene group.), Etc., and is preferably —COO—R ³⁶ —.

Examples of the counter anion M ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .
Moreover, the partial structure containing the said specific quaternary ammonium base may be contained 2 or more types in one B block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. Furthermore, the partial structure which does not contain the quaternary ammonium base may be contained in the B block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later, etc. Is mentioned. The content of the partial structure containing no quaternary ammonium base in the B block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. It is most preferable that it is not contained in.

In addition, the B block of the acrylic block copolymer described above may have some tertiary amino groups. This remains when the quaternization reaction of the tertiary amino group is not completely completed, and its amine value is usually about 10 mgKOH / g or less.
On the other hand, when the B block constituting the acrylic block copolymer includes a primary to tertiary amino group, the content ratio of the monomer having the primary to tertiary amino group constitutes the copolymer. In the monomer composition, it is preferably 20 mol% or more, more preferably 50 mol% or more.

The primary to tertiary amino group is preferably —NR ⁴¹ R ⁴² (wherein R ⁴¹ and R ⁴² each independently represents a cyclic or chain alkyl group which may have a substituent, An aryl group which may have a substituent or an aralkyl group which may have a substituent is preferable. As a partial structure including this (repeating unit), preferred examples include the following: A structure represented by the general formula can be given.

(However, R ⁴¹ and R ⁴² have the same meanings as R ⁴¹ and R ⁴² described above, R ⁴³ represents an alkylene group having 1 or more carbon atoms, and R ⁴⁴ represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably a methyl group, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a hydrogen atom or a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following general formula is particularly preferably used.

(In the above general formula, R ⁴⁴ has the same meaning as described above.)
Furthermore, the partial structure containing the said amino group may be contained 2 or more types in one B block. In that case, two or more amino group-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. Moreover, a partial structure not containing an amino group may be partially contained in the B block, and examples of such a partial structure include a partial structure derived from a (meth) acrylate monomer. . The content of such a partial structure not containing an amino group in the B block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably it is not included.

  In addition, the solvophilic A block constituting the block copolymer of the (e-2) dispersant does not have a nitrogen atom-containing functional group such as an amino group as described above, and is a monomer constituting the B block as described above. There is no particular limitation as long as it is composed of a monomer that can be copolymerized with. The A block is a solvophilic site that does not have a nitrogen atom-containing functional group that serves as a pigment adsorbing group, and has an affinity for the solvent, and thus has a function of stabilizing the pigment adsorbed on the dispersant in the solvent. .

  Examples of the solvophilic A block include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol ( (Meth) acrylate monomers such as (meth) acrylate and polypropylene glycol (meth) acrylate; polyalkylene glycols such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate Vinyl acetate monomers; (meth) (meth) acrylate monomers such as acrylic acid chloride allyl glycidyl ether, polymer structure in which the comonomer is copolymerized, such as glycidyl ether monomers such as crotonic acid glycidyl ether.

Among these, as the A block, those containing a (meth) acrylic acid ester monomer as a copolymerization component are preferable. Also preferred are those containing polyalkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate as copolymerization components (that is, containing a partial structure derived from polyalkylene glycol (meth) acrylate). . Further, when the dispersant used in the composition for forming a color filter pixel of the present invention is a (meth) acrylic copolymer, the following general formula (VIII)
The A block having a partial structure represented by

(In the general formula (VIII), n represents an integer of 1 to 5, but when there are a plurality of the units, that is, the general formula (VIII) in one molecule, n may be the same or different. R ⁸¹ represents a hydrogen atom or a methyl group, R ⁸² represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁸² is particularly preferably an ethyl group.)
The partial structure represented by the general formula (VIII) is preferably contained in an amount of 3 to 20 mol% in terms of monomers constituting the (meth) acrylic copolymer. It is most preferable that 10 mol% is contained.

Although the detailed mechanism of action is unclear, by having a partial structure derived from polyalkylene glycol (meth) acrylate, particularly a partial structure represented by the above general formula, it is possible to improve hydrogen bonding properties and disperse It is considered that the affinity with the solvent is improved and the stability of the dispersion system is increased.
Two or more partial structures represented by the general formula (VIII) may be contained in one A block. Of course, the A block may further contain a partial structure other than these. When partial structures derived from two or more types of monomers are present in the A block, each partial structure may be contained in the A block in any form of random copolymerization or block copolymerization.

The dispersant (C-2) that can be used in the pigment dispersion of the present invention is an AB block or ABA block copolymeric polymer compound composed of an A block and a B block as described above. Of these, AB block copolymers are preferred. Such a block copolymer is prepared, for example, by a living polymerization method.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Specifically, for example, a method described in JP-A-2007-270147 can be mentioned.

The amine value of 1 g of the above (C-2) dispersant is usually about 1 to 300 mgKOH / g in terms of effective solid content, but the preferred range is not the case where the B block has a quaternary ammonium base. It depends on the case.
That is, when the B block of the AB block copolymer and ABA block copolymer of the (C-2) dispersant has a quaternary ammonium base, the amount of the quaternary ammonium base in 1 g of the copolymer is 0. It is preferable that it is 1-10 mmol. Outside this range, it may not be possible to combine good heat resistance and dispersibility. In such a block copolymer, an amino group generated in the production process may be contained, and its amine value is usually about 1 to 100 mgKOH / g, preferably 1 to 50 mgKOH per 1 g of the copolymer. / G, more preferably 1 to 30 mg KOH / g.

  When the quaternary ammonium base is not included in the B block, the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g, more preferably 80 mgKOH / g or more and 150 mgKOH. / G or less, more preferably 90 to 150 mgKOH / g, and most preferably 100 to 140 mgKOH / g.

If the number of functional groups containing nitrogen atoms is too small, the adsorptive power of the dispersant molecules on the pigment surface may be insufficient, and it may be difficult to obtain sufficient dispersion stability. On the other hand, if the amine value is too high, the molecular weight of the A block becomes relatively small, and the dispersion stability may be insufficient.
The acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably lower, usually 100 mgKOH / g or less, preferably 50 mgKOH / g or less. , More preferably 40 mgKOH / g or less, most preferably 30 mgKOH / g or less. The molecular weight is usually in the range of 1000 or more and 100,000 or less in terms of polystyrene-equivalent weight average molecular weight (Mw) measured by GPC.

In the present invention, a commercially available (meth) acrylic block copolymer having the same structure as that described above can also be used.
<Other dispersants>
(C) As a dispersing agent, it contains dispersing agents other than the above-mentioned various (C-1) and (C-2) dispersing agents (hereinafter, may be referred to as (C-3) dispersing agent). Also good.

  (C-3) Examples of the dispersant include a urethane-based dispersant, a polyallylamine-based dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether-based dispersant, and a polyoxyethylene diester-based dispersant. Examples thereof include a dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

  Specific examples of such a dispersant include EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol), KP (manufactured by Shinetsu) Chemical products), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and other series names can be mentioned.

In addition, the above-mentioned (C-1) dispersing agent-(C-3) dispersing agent may be used individually by 1 type, or may use 2 or more types together.
In the present invention, when the pigment dispersion further contains (C) a dispersant, the content of the (C) dispersant is preferably about 0 to 200% by weight based on (A) the pigment. It is more preferable to use about 150% by weight.

(C) By controlling the content ratio of the dispersing agent within this range, a necessary and sufficient amount of the dispersing agent adheres to the pigment surface. Therefore, aggregation is performed without reducing the coloring power of the colored resin composition described later. It can be effectively prevented, and high viscosity or gelation can be avoided, so that high dispersion stability can be ensured.
<Dispersing aid>
The pigment dispersion of the present invention may further contain a dispersion aid. Examples of the dispersion aid, that is, a pigment derivative, include, for example, JP-A No. 2001-220520, JP-A No. 2001-271004, JP-A No. 2002-179976, JP-A No. 2007-113000, and JP-A No. 2007. Various compounds described in JP-A-186681 and the like can be used.

  When the pigment dispersion of the present invention further contains a dispersion aid, the amount added is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20%, based on the pigment (A). % By weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less. By controlling the addition amount within the above range, the effect as a dispersion aid is exhibited, and it is possible to prevent the dispersibility and dispersion stability from being deteriorated.

<Dispersed resin>
The pigment dispersion of the present invention may contain a part or all of a resin selected from (D) binder resin or other binder resin described later as the following dispersion resin.
Specifically, in the dispersion treatment step to be described later, the (D) binder resin is added to the (C) dispersant by adding the (D) binder resin together with the components such as the (C) dispersant described above. It contributes to the dispersion stability of the pigment (A) by a synergistic effect. As a result, there is a possibility that the amount of (C) dispersant added may be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.

As described above, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of pigment in the pigment dispersion.
As the dispersion resin, various (D) binder resins described later can be used.
The acid value of the dispersion resin is preferably 0 mgKOH / g or more, more preferably 1 mgKOH / g or more, most preferably 5 mgKOH / g or more, more preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less. Most preferred. By controlling the acid value within the above range, the alkali developability is improved, and the handling becomes easy in synthesis and the like.

  The weight average molecular weight in terms of polystyrene measured by GPC of the dispersion resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, more preferably 200000 or less, more preferably 50000 or less, and 30000 or less. Most preferred. By controlling the molecular weight within the above range, the alkali developability can be improved and the dispersion stability can be prevented from being lowered.

<Colored resin composition>
The colored resin composition of the present invention contains at least the above-described (A) pigment, (B) an alkaline earth metal salt of a water-soluble dye having an acidic group, and the following (D) binder resin, and if necessary, You may contain additives other than these components. Moreover, it is especially preferable to contain the solvent mentioned later, (E) polymerizable monomer, (F) photopolymerization initiators, and / or thermal polymerization initiators.

The colored resin composition of the present invention may be prepared by mixing other components with a pigment dispersion prepared in advance, or all components may be mixed simultaneously or sequentially. .
As components other than these essential components, in addition to the various components described in the present specification, any components that can be used as a color filter forming material can be used without particular limitation.

<(D) Binder resin>
The (D) binder resin used in the colored resin composition of the present invention can be used without particular limitation as long as it can be used for pixel formation of a color filter. For example, a thermosetting resin composition used in a manufacturing process of a so-called lift-off type color filter described in JP-A-60-184202 or the like, or an ink-jet type color filter described in JP-A-2004-220036 or the like Examples thereof include a resin contained in a thermosetting resin composition used in the production process, a photopolymerizable resin described later, and the like.

However, in view of the effect of the present invention, the (D) binder resin is preferably selected from binder resins used for the formation of color filter pixels by photolithography.
Examples of such binder resins include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, and JP-A-2000-56118. Various polymer compounds described in JP-A No. 2003-233179, JP-A No. 2007-270147, and the like can be used.
(D-1): obtained by reacting a monomer containing an ethylenically unsaturated group containing a mono (meth) acrylate having a specific structure and an epoxy group-containing (meth) acrylate or (meth) acrylic acid ( (Meth) acrylic alkali-soluble resin,
(D-2): a linear alkali-soluble resin containing a carboxyl group in the main chain,
(D-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the carboxyl group-containing resin,
(D-4): (Meth) acrylic resin and the like.

Among these, the resin described in (D-1) is particularly preferable.
Hereinafter, each of these resins will be described.
<(D-1) Obtained by reacting a mono (meth) acrylate having a specific structure and an ethylenically unsaturated group-containing monomer containing an epoxy group-containing (meth) acrylate or (meth) acrylic acid ( (Meth) acrylic alkali-soluble resin>
Among (D) binder resins used in the colored resin composition of the present invention, as a particularly preferable (D) binder resin, “a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer” On the other hand, it is obtained by adding a polybasic acid anhydride to a resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the copolymer or to at least a part of the hydroxyl group generated by the addition reaction. Resin (hereinafter sometimes referred to as (D-1) resin) ”.

More specifically, as the (D-1) resin, for example, a (meth) acrylic copolymer (D-) using a mono (meth) acrylate having a specific alicyclic hydrocarbon group described below. 1-1) to (D-1-3) are preferable. Among these, the (meth) acrylic copolymer described in the following (D-1-1) is more preferable because it is particularly effective for suppressing reduction in luminance of the pixel.
<(D-1-1) (a) An ethylenically unsaturated group-containing unit containing a mono (meth) acrylate having a structure represented by the following general formula (D1) and (b) an epoxy group-containing (meth) acrylate (Meth) acrylic copolymer obtained by reacting a monomer (hereinafter sometimes referred to as (D-1-1) copolymer)>
The (D-1-1) copolymer has (a) a partial structure derived from mono (meth) acrylate having a structure represented by the following general formula (D1) as an essential component.

In the general formula (D1), R ^{91 to} R ⁹⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁹⁵ to R ⁹⁸ each independently represent a hydrogen atom or 1 carbon atom. Or an alkyl group of ˜3, or may be linked to each other to form a ring.
In the general formula (D1), the ring formed by connecting R ⁹⁵ and R ⁹⁶ and R ⁹⁷ and R ⁹⁸ is preferably an aliphatic ring, and may be either saturated or unsaturated. It is preferable that carbon number is 5-6.

  Especially, as a structure represented by general formula (D1), what is represented by the following structural formula (D1a), (D1b), or (D1c) is preferable.

  (D-1-1) By introducing these structures into the resin, when the colored resin composition of the present invention is used for a color filter or a liquid crystal display element, the heat resistance of the colored resin composition is improved. Or the strength of a pixel formed using the colored resin composition can be increased.

In addition, the mono (meth) acrylate which has a structure represented by the said general formula (D1) may be used individually by 1 type, and may use 2 or more types together.
In addition, as the mono (meth) acrylate having the structure represented by the general formula (D1), various known ones can be used as long as the structure has the structure, and particularly represented by the following general formula (D2). Those are preferred.

In the general formula (D2), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the general formula (D1).
The (D-1-1) copolymer has a partial structure derived from (b) an epoxy group-containing (meth) acrylate (hereinafter sometimes referred to as (b1) an epoxy group-containing (meth) acrylate) as an essential component. And

  (B1) Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl. Examples include (meth) acrylate glycidyl ether. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

A known solution polymerization method is applied to the copolymerization reaction of (a) mono (meth) acrylate having the structure represented by the general formula (D1) and (b1) epoxy group-containing (meth) acrylate. Is done. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
The usage-amount of a solvent is 30-1000 weight part normally with respect to 100 weight part of obtained (D-1-1) copolymers, Preferably it is 50-800 weight part. If the amount of the solvent used is outside this range, it will be difficult to control the molecular weight of the copolymer.

The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst is used. be able to.
Among radical polymerization initiators using an organic peroxide catalyst or an azo compound catalyst, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 weight part with respect to a total of 100 weight part of the monomer used for a copolymerization reaction, Preferably it is 1-10 weight part.

  The copolymerization reaction may be performed by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring, or by adding the monomer to which the radical polymerization initiator is added. Alternatively, the reaction may be performed dropwise in a solvent that has been heated and stirred. Alternatively, the monomer may be added dropwise while the radical polymerization initiator is added to the solvent and the temperature is raised. The reaction conditions can be freely changed according to the target molecular weight.

In addition, a copolymer obtained by reacting (a) a mono (meth) acrylate having a structure represented by the general formula (D1) and (b1) an epoxy group-containing (meth) acrylate as the essential components described above, Further, (e) a partial structure derived from another monomer may be contained.
(E) There is no restriction | limiting in particular as another monomer, What is necessary is just a compound which can be copolymerized with (a), (b1), and (b2) (meth) acrylic acid.

  Specifically, for example, vinyl aromatics such as styrene, styrene α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; butadiene, 2,3-dimethylbutadiene, isoprene, Dienes such as chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (Meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid isoamyl, (meth) acrylic acid hexyl, (meta ) -2-ethylhexyl acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Cyclopentyl acid, cyclohexyl (meth) acrylate, (meth) acrylate-2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, propargyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid naphthyl, (meth) acrylic acid anthracenyl, (meth) acrylic acid anthraninonyl, (meth) acrylic acid piperonyl, (meth) acrylic acid salicylate, (meth) acrylic acid furyl, (Meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofuryl, (meth) acrylic acid pyranyl, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl, (meth) acrylic acid cresyl, (meth) acrylic acid-1 , 1,1-trifluoro Ethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, (Meth) acrylic acid esters such as (meth) acrylic acid 3- (N, N-dimethylamino) propyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl; ) Acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N- (Meth) acrylic amides such as di-iso-propylamide, (meth) acrylic acid anthracenyl amide; Vinyl compounds such as anilide, methacryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate; diethyl citraconic acid, diethyl maleate, Unsaturated dicarboxylic acid diesters such as diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; N- (meta ) Acrylyl phthalimide and the like.

(E) Among other monomers, in order to impart excellent heat resistance, coating strength, and pigment dispersibility to the colored curable resin composition, (such as styrene, benzyl (meth) acrylate) e1) An ethylenically unsaturated monomer having an aromatic hydrocarbon group is preferred.
When the partial structure derived from this (e1) ethylenically unsaturated monomer having an aromatic hydrocarbon group is contained in the (D-1-1) copolymer, the content is 1 to 70 mol%. Some are preferred, and more preferably 3 to 50 mol%.

<(D-1-2) (a) An ethylenically unsaturated group-containing unit containing a mono (meth) acrylate having a structure represented by the general formula (D1) and (b1) an epoxy group-containing (meth) acrylate Polymers are obtained to obtain a trunk resin, and (c) an unsaturated monobasic acid is reacted with at least part of the epoxy group derived from (b1) in the trunk resin, and (d) at least part of the resulting hydroxyl group. A (meth) acrylic copolymer obtained by reacting a polybasic acid or an anhydride thereof. > In the present invention, the resin (D-1) that can be used is the above-mentioned “(a) mono (meth) acrylate having the structure represented by the general formula (D1) and (b1) epoxy group-containing (meth)”. At least a part of the epoxy group derived from (b1) of the (meth) acrylic copolymer obtained by reacting acrylate (and (e) other monomer as necessary) (c) A copolymer (hereinafter referred to as (D-1-2) copolymer) obtained by reacting a saturated monobasic acid and reacting (d) a polybasic acid anhydride with at least part of the resulting hydroxyl group. May be).

  (C) As unsaturated monobasic acid, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned. Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These (c) unsaturated monobasic acids may be used alone or in combination of two or more. By adding such components, polymerizability can be imparted to the (D) binder resin used in the present invention.

  These (c) unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group derived from (b1) in the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. Add to mol%. (C) When the addition ratio of unsaturated monobasic acid is too small, wetting and spreading may be insufficient. In addition, as a method of adding (c) unsaturated monobasic acid to the epoxy group of a copolymer, a well-known method is employable.

  Furthermore, when (c) an unsaturated monobasic acid is added to an epoxy group derived from (b1), a known one can be used as the (d) polybasic acid or anhydride thereof added to the resulting hydroxyl group. For example, dibasic acids such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, chlorendic acid; trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid Examples of the acid include bases or higher and anhydrides thereof.

Of these, acid anhydrides are preferable, and tetrahydrophthalic anhydride and / or succinic anhydride are particularly preferable. These (d) polybasic acids or anhydrides thereof may be used alone or in combination of two or more. .
These (d) polybasic acids or anhydrides thereof are usually 10 to 100 mol of hydroxyl groups generated by adding (c) unsaturated monobasic acid to the epoxy group derived from (b1) of the copolymer. %, Preferably 20 to 90 mol%, more preferably 30 to 80 mol%. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

  Furthermore, when the colored resin composition of the present invention is a photopolymerizable composition, in order to improve the sensitivity to light, after adding the above-mentioned polybasic acid anhydride, one of the generated carboxyl groups is added. Glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to the part. Moreover, in order to improve developability, you may add the glycidyl ether compound which does not have a polymerizable unsaturated group to some produced | generated carboxyl groups. Both of these may be added.

  Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group. As commercial products, for example, trade names “Denacol EX-111”, “Denacol EX-121”, “Denacol EX-141”, “Denacol EX-145”, “Denacol EX-146”, “Denacol EX-146” manufactured by Nagase Chemical Industries, Ltd. Denacol EX-171 "," Denacol EX-192 "and the like.

Incidentally, the trunk resin in the (D-1-2) copolymer also has a partial structure derived from the above-mentioned (e) other monomer, as in the (D-1-1) copolymer. You may do it. (E)
Examples of the other monomer include the same compounds as in the (D-1-1) copolymer. Also preferred are ethylenically unsaturated monomers having (e1) aromatic hydrocarbons such as styrene and benzyl (meth) acrylate.

<(D-1-3) (a) Mono (meth) acrylate having a structure represented by the general formula (D1) and (b2) an ethylenically unsaturated group-containing monomer containing (meth) acrylic acid (Meth) acrylic copolymer obtained by reacting
In the present invention, (D-1) resin that can be used as (D) binder resin includes (a) mono (meth) acrylate having the structure represented by the general formula (D1), and (b2) (meth) acrylic. Even a (meth) acrylic copolymer (hereinafter sometimes referred to as a (D-1-3) copolymer) obtained by reacting an ethylenically unsaturated group-containing monomer containing an acid. Good.

  The (D-1-3) copolymer may also have a partial structure derived from (e) another monomer as described above, similarly to the (D-1-1) copolymer. (E) Other monomers include the same compounds as described in the section of (D-1-1) copolymer, and among them, (e1) aromatics such as styrene and benzyl (meth) acrylate Ethylenically unsaturated monomers having hydrocarbons are preferred.

When the partial structure derived from this (e1) ethylenically unsaturated monomer having an aromatic hydrocarbon group is contained in the (D-1-3) copolymer, the content is 1 to 70 mol%. Some are preferred, and more preferably 3 to 50 mol%.
In addition, it is preferable that the polystyrene equivalent weight average molecular weight (Mw) measured by GPC of (D-1) resin used for the colored resin composition of this invention is 3000-100000, and is 4000-50000. It is more preferable. If the molecular weight is less than 3000, heat resistance and film strength may be inferior, and if it exceeds 100,000, the solubility in a developer tends to be insufficient. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

Moreover, the acid value of (D-1) resin used for the colored resin composition of this invention is 10-200 mgKOH / g normally, Preferably it is 15-150 mgKOH / g, More preferably, it is 25-100 mgKOH / g.
<(D-2) A linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter sometimes referred to as (D-2) resin)>
(D-2) The linear alkali-soluble resin containing a carboxyl group in the main chain is not particularly limited as long as it has a carboxyl group, and usually obtained by polymerizing a polymerizable monomer containing a carboxyl group. It is done.

Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl adipic acid. 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- ( (Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxybutyl Succinic acid, 2- (me ) Vinyl monomers such as acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; -Monomers obtained by adding lactones such as caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone; hydroxyalkyl (meth) acrylate to succinic acid, maleic acid, phthalic acid, or anhydrides thereof And monomers added with acids or anhydrides. A plurality of these may be used.

Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.
Moreover, (D-2) resin may copolymerize the other polymerizable monomer which does not have a carboxyl group with said carboxyl group-containing polymerizable monomer.
Examples of other polymerizable monomers include, but are not limited to, those described in JP-A-2009-52010. Of these polymerizable monomers, a copolymer resin containing benzyl (meth) acrylate is particularly preferred from the viewpoint of excellent pigment dispersibility.

  In addition, the acid value of (D-2) resin used for the colored resin composition of this invention is 30-500 mgKOH / g normally, Preferably it is 40-350 mgKOH / g, More preferably, it is 50-300 mgKOH / g. Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-20000 normally, Preferably it is 3000-50000, More preferably, it is 4000-30000.

<Resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin of (D-3) (D-2) (hereinafter sometimes referred to as (D-3) resin)>
A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the linear alkali-soluble resin containing a carboxyl group in the main chain (D-2) is also preferable.
The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.

  For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- An acyclic epoxy group-containing unsaturated compound such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but an alicyclic epoxy group-containing unsaturated compound is preferred from the viewpoint of heat resistance and pigment dispersibility.

  Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5 .2.1.0] dec-2-yl] group and the like. Further, the ethylenically unsaturated group is preferably derived from a (meth) acryloyl group.

The general formulas (3a) to (3m), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkylene group, R ¹³ represents a divalent hydrocarbon group, and n represents an integer of 1 to 10. .
In the general formulas (3a) to (3m), the alkylene group represented by R ¹² preferably has 1 to 10 carbon atoms.
Specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group, and a methylene group, an ethylene group, and a propylene group are preferable.

As the hydrocarbon group R ^13, preferably has 1 to 10 carbon atoms, alkylene group, a phenylene group, and the like. These alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
Among these, a compound represented by the general formula (3c) is preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.

  Various methods can be used to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (D-2). For example, a carboxyl group-containing resin and an epoxy group-containing unsaturated compound are converted into a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride A quaternary ammonium salt such as pyridine, triphenylphosphine, etc., in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours. Saturated compounds can be introduced.

  The acid value of the carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 mgKOH / g, preferably 20 to 150 mgKOH / g, more preferably 30 to 150 mgKOH / g. Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-100000 normally, Preferably it is 4000-50000, More preferably, it is 5000-30000.

<(D-4) (Meth) acrylic resin (hereinafter sometimes referred to as (D-4) resin)>
Examples of the (meth) acrylic resin include a polymer obtained by polymerizing a monomer component essentially including a compound represented by the following general formula (D41) described in JP-A-2006-161035.

(In the general formula (D41), R ^1a and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
The colored resin composition of the present invention may contain a binder resin other than the above-mentioned (D-1) to (D-4) resins as long as the effects of the present invention are not impaired. Moreover, as (D) binder resin used for the colored resin composition of this invention, 1 type may be used independently among the above-mentioned various resins, and 2 or more types may be used together.

  Further, the content ratio of the total amount of (D) binder resin is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 80% by weight or less, preferably 60% by weight or less in the total solid content. is there. (D) When there is too little content of binder resin, a film | membrane will become weak and the adhesiveness to a board | substrate may fall. On the other hand, when the amount is too large, the permeability of the developing solution to the exposed portion increases, and the surface smoothness and sensitivity of the pixel may deteriorate.

<Solvent>
In the present invention, the solvent has a function of adjusting viscosity by dissolving or dispersing components other than the above components in addition to the above components.
There is no restriction | limiting in particular as a solvent, What is necessary is just a thing which can melt | dissolve or disperse | distribute each component. Examples of such a solvent include the solvents described in International Publication WO2009 / 107734 and the like.

  Commercially available products corresponding to these solvents include mineral spirits, valsol # 2, Apco # 18 solvent, apco thinner, and soak solvent no. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like. These solvents may be used alone or in combination of two or more.

In addition, the content ratio of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by weight or less, and preferably 50% by weight considering the viscosity suitable for coating. Above, more preferably 60% by weight or more, particularly preferably 70% by weight or more.
<(E) Polymerizable monomer>
The colored resin composition of the present invention may further contain components other than those described above as necessary. Examples of such components include (E) polymerizable monomer, (F) photopolymerization initiators and / or thermal polymerization initiators, surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents. , Adhesion improvers, development improvers, dyes and the like.

Examples of the polymerizable monomer (E) include those described in International Publication WO2009 / 107734 and the like.
These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.

  A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel tends to be inferior. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

  More preferred polyfunctional monomers having acid groups are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol pentaacrylate succinic acid ester, which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is. Other polyfunctional monomers can be used in combination with this polyfunctional monomer.

(E) The blending ratio of the polymerizable monomer is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 80% by weight in the total solid content of the colored resin composition of the present invention. % Or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
<(F) Photopolymerization initiators and / or thermal polymerization initiators>
The colored resin composition of the present invention preferably further contains (F) a photopolymerization initiator and / or a thermal polymerization initiator for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.

  In particular, when the colored resin composition of the present invention contains (D) a resin having an ethylenic double bond as a binder resin component, or (E) when an ethylenic compound is contained as a polymerizable monomer component described above, Photopolymerization initiators that have the function of directly absorbing light or being photosensitized to cause decomposition reaction or hydrogen abstraction reaction to generate polymerization active radicals, and / or thermal polymerization initiation that generates polymerization active radicals by heat It is preferable to contain agents.

In the present invention, the component (F) as the photopolymerization initiator is a photopolymerization initiator (hereinafter sometimes referred to as the (F-1) component) or a polymerization accelerator (hereinafter referred to as (F-). 2) or a sensitizing dye (hereinafter sometimes referred to as the component (F-3)), or the like.
<Photopolymerization initiators>
The (F) photopolymerization initiators that may be contained in the colored resin composition of the present invention are usually (F-1) a photopolymerization initiator and (F-3) added as required. A function that is used as a mixture with an additive such as a dye-sensitizing agent and (F-2) a polymerization accelerator and directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical It is a component having

  (F) Photopolymerization initiators (F-1) Examples of photopolymerization initiators include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; Hexaarylbiimidazole derivatives described in JP-A-10-300922, JP-A-11-174224, JP-A-2000-56118, etc .; Halomethylated oxadiazoles described in JP-A-10-39503 Derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP 2000-80068 A and the like .

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 and the like.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

  Moreover, the colored resin composition of this invention can mix | blend (F-2) a polymerization accelerator further as needed, especially when (F) photoinitiators are included. (F-2) Examples of the polymerization accelerator include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2 -Mercapto compounds having a heterocyclic ring such as mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

One of these (F-1) photopolymerization initiator and (F-2) polymerization accelerator may be used alone, or two or more thereof may be used in combination.
In the colored resin composition of the present invention, (F-3) a sensitizing dye may be used in the photopolymerization initiators (F-3) for the purpose of increasing the sensitivity. (F-3) As the sensitizing dye, an appropriate dye is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc. A coumarin dye having a heterocyclic ring described in JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin described in JP-A-3-239703, JP-A-5-289335, etc. Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A 47-2528, JP-A 54-155292, JP-B 45-37377, JP-A 48-84183, JP 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP No. 5-107761, JP-A-5-210240, it may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

Among these (F-3) sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. (F-3) Particularly preferred as the sensitizing dye is, for example, compounds described in JP-A-2009-25813.
(F-3) A sensitizing dye may also be used alone or in combination of two or more.

In the colored resin composition of the present invention, the content ratio of these (F) photopolymerization initiators ((F-1) photopolymerization initiator, (F-2) polymerization accelerator and (F-3) sensitizing dye). The total solid content is usually 0% by weight or more, preferably 0.1% by weight or more, and usually 40% by weight or less, preferably 30% by weight or less.
<Thermal polymerization initiators>
Specific examples of the thermal polymerization initiators that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used.

Specific examples of the azo compound, organic peroxide, and hydrogen peroxide include compounds described in JP-A-2009-7560.
In addition, some of the above-described (F-1) photopolymerization initiators also function as thermal polymerization initiators such as α-aminoalkylphenone derivatives. Therefore, you may use the compound selected from the examples given as an example of (F-1) photoinitiator as a thermal-polymerization initiator.

These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.
In the present invention, the content ratio of the thermal polymerization initiators is preferably 0 to 30% by weight, particularly preferably 0 to 20% by weight, based on the total solid content of the colored resin composition.
<Surfactant>
The colored resin composition of the present invention may further contain a surfactant. Various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, but they may adversely affect various properties such as voltage holding ratio and compatibility with organic solvents. It is preferable to use a nonionic surfactant in terms of low properties.

As the surfactant, for example, those described in JP-A-2009-25813 can be used.
The content of these surfactants is preferably 0.001% by weight or more, more preferably 0.005% by weight or more, and still more preferably 0.01% by weight in the total solid content of the colored resin composition of the present invention. That's it. Further, it is preferably used in the range of 10% by weight or less, more preferably 5% by weight or less, and still more preferably 1% by weight or less.

<Preparation method of pigment dispersion and colored resin composition>
The colored resin composition of the present invention may be prepared by mixing the materials constituting the composition at once or sequentially. However, as described below, a pigment dispersion is prepared in advance, It is preferred to mix the components.
Hereinafter, although an example of the method of preparing the pigment dispersion liquid and colored resin composition of this invention is demonstrated, there is no restriction | limiting in particular in a preparation method, It is not necessarily limited to the method described below.

Further, as described above, the pigment dispersion and the colored resin composition of the present invention are preferably used as a pigment dispersion for a color filter and a colored resin composition from the viewpoint of “effect of the present invention” and the like. Specifically, it is preferably used as a material for forming a pixel of a color filter.
The pigment dispersion and the colored resin composition of the present invention may be photocurable (photopolymerizable) or thermopolymerizable depending on the color filter production process to be applied.

The colored resin composition of the present invention is a pigment dispersion comprising at least (A) a pigment, (B) an alkaline earth metal salt of a water-soluble dye having an acidic group, and optionally a dispersion resin, a solvent, and the like. It is preferable to prepare this by mixing other components such as (D) a binder resin, and optionally used (E) polymerizable monomer.
The alkaline earth metal salt of the water-soluble dye having an acidic group (B) in the present invention is particularly preferably used in the atomization step and / or the dispersion treatment step.
Examples of the atomization step include a grinding method in which pigments and additives are mechanically pulverized to reduce the particle size. In the grinding method, the pigments and / or additives are ground using a ball mill, sand mill or kneader, with a water-soluble inorganic salt such as sodium chloride as a grinding agent, and optionally a water-soluble organic solvent that does not dissolve them. A relatively uniform pigment and / or additive particle can be obtained by removing the grinding agent and the water-soluble organic solvent by washing or the like to make the primary particles finer. However, although the phenomenon that the pigment fine particles are crystallized easily by energy such as heat generated during the atomization step is likely to occur, in the present invention (B) this phenomenon occurs in the presence of an alkaline earth metal salt of a water-soluble dye having an acidic group. Can be suppressed.
In the dispersion treatment step, (A) the pigment is dispersed to form an ink-like liquid (pigment dispersion or pigment dispersion). In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By carrying out this dispersion treatment, the pigment is made fine, so that the coating characteristics of the colored resin composition are improved and the transmittance of the product color filter substrate and the like is improved.

  When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition of the ink-like liquid and the size of the sand grinder apparatus.

  In the pigment dispersion obtained by the above dispersion treatment, (D) a binder resin, and optionally used (E) polymerizable monomer, (F) photopolymerization initiators, and / or thermal polymerization initiators, surface activity A colored resin composition is obtained by mixing other components such as an agent to obtain a uniform dispersion solution. In addition, in each process of a dispersion | distribution process and a mixing process, since fine refuse may mix, it is preferable to filter the obtained ink-like liquid with a filter etc.

<Application of colored resin composition>
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. This is supplied onto the substrate to form a color filter and a component of the display device.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a pixel of a color filter, a liquid crystal display device (panel) and an organic EL display using them will be described.

<Manufacture of color filter substrates>
Next, the color filter of the present invention (hereinafter sometimes referred to as “color filter substrate”) will be described.
The color filter of the present invention is characterized by having pixels formed on the substrate using the above-described colored resin composition.

<Transparent substrate (support)>
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic. Examples thereof include thermosetting resin sheets such as a resin, or various glasses. Among these, glass or heat resistant resin is preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, for improvement of surface properties such as adhesion, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, etc. May be performed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, and is 10 micrometers or less normally, Preferably it is the range of 5 micrometers or less.

<Black Matrix>
The color filter according to the present invention can be manufactured by providing a black matrix on the above-described transparent substrate and further forming pixel images of red, green and blue colors. The colored resin composition of the present invention is used as a coating liquid for forming pixels which are usually red, green and blue.

The black matrix is formed on the transparent substrate using a light shielding metal thin film or a coating liquid for forming a black matrix (which may be the colored resin composition of the present invention). As the light shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, and the like may be used, and these may be laminated in a plurality of layers.
These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate and perchloric acid and / or nitric acid are applied to chromium. Other materials are etched using an etchant appropriate for the material, and finally the positive photoresist is stripped with a special stripper to form a black matrix. can do.

  In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the colored resin composition on the thin film, the coating film is exposed and developed using a photomask having a repeated pattern such as stripes, mosaics, and triangles to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

  When using a black matrix forming coating solution, a black matrix is formed using a colored resin composition containing a black pigment. For example, black pigments such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc., alone or in combination, or a mixture of red, green, blue, etc., appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed in the same manner as in the following method for forming red, green and blue pixel images using a colored resin composition containing a black pigment.

  When a color filter (pixels) is manufactured by an ink jet method, a partition pattern (black matrix) is first provided on a substrate, and pixels are formed in the pattern (hereinafter sometimes referred to as “inside a pixel bank”). Ink (colored resin composition) is directly applied to produce a color filter. Since ink droplets can be drawn at a desired position, high productivity and cost reduction of the color filter can be achieved.

The black matrix of the color filter by the ink jet method not only functions as a light blocking function that is conventionally required, but also functions as a partition to prevent the RGB ink driven into the pixel bank from being mixed. The film thickness is thicker than that of the color filter according to (1). Usually, the film thickness is 1.5 μm or more, preferably about 1.8 to 2.5 μm, more preferably about 2.0 to 2.3 μm. ). In addition, in order to prevent color mixing of RGB ink, liquid repellent treatment is often applied to the upper surface of the black matrix.

Therefore, it was formed using a photosensitive material including a black color material from a conventionally used chromium compound such as chromium, chromium oxide and chromium nitride, and a black matrix made of a light-shielding metal material such as nickel and tungsten alloy. A resin black matrix is preferred.
When the color filter of the present invention is produced by the inkjet method, the resin black matrix may be formed by a general photolithography method using the photosensitive coloring resin composition for black matrix as described above. Subsequently, the surface of the transparent substrate is made hydrophilic and the black matrix pattern is made liquid repellent by chemical treatment or physical treatment, respectively.

<Formation of pixels>
The method for forming the pixel varies depending on the type of the colored resin composition to be used. First, a case where a photopolymerizable composition is used as the colored resin composition and pixels are formed by photolithography will be described as an example.
On a transparent substrate provided with a black matrix, a colored resin composition of one of red, green, and blue is applied and dried, and then a photomask is overlaid on the coating film, and image exposure is performed through this photomask. A pixel image is formed by development and, if necessary, thermal curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation for each of the three colored resin compositions of red, green, and blue.

  The colored resin composition can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, and there is no influence of mist adhering when using the spin coating method. It is preferable from a viewpoint.

  If the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell forming process may be difficult. On the other hand, if it is too small, it is difficult to increase the pigment concentration. Color expression may be impossible. The thickness of the coating film is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm as the film thickness after drying. The range is as follows.

Next, a case where pixels are formed by an inkjet method will be described.
In the pixel bank on the substrate provided with the resin black matrix, the colored resin composition of the present invention is used to draw with an inkjet apparatus, and the composition is completely cured by drying, photocuring and / or heat curing, A color filter is obtained by forming pixels. In addition, as the colored resin composition for pixel formation, three colors of R (red), G (green), and B (blue) are often used, but are not limited thereto.

<Drying of coating film>
Drying of the coating film formed by applying the colored resin composition to the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried.
The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 The drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter.

  The temperature condition for reheat drying is preferably higher than the pre-drying temperature. Specifically, it is usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably 130 ° C. It is the range below ℃. Moreover, although it depends on the heating temperature, the drying time is usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, preferably 5 minutes. The higher the drying temperature, the better the adhesion to the transparent substrate. However, if the drying temperature is too high, the polymer may be decomposed to cause thermal polymerization and cause poor development. In addition, as a drying process of this coating film, you may use the reduced pressure drying method which dries in a reduced pressure chamber, without raising temperature. Preferred drying conditions are 0.1 to 1 Torr, and the drying time is in the range of 10 seconds to 60 minutes.

Moreover, when the colored resin composition of this invention is photopolymerizable, an exposure process is performed following this drying process.
<Exposure process>
Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating an ultraviolet or visible light source through the mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen.

  The light source used for said image exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples thereof include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

When the color filter of the present invention is produced by photolithography, the process further proceeds to a development process.
<Development process>
The color filter of the present invention uses an organic solvent or an aqueous solution containing a surfactant and an alkaline compound after image exposure with the above-mentioned light source to the coating film using the colored resin composition of the present invention. By performing development in this manner, an image can be formed on the substrate and manufactured. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, phosphorus Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- Or trimethylamine, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline Organic alkali compound may be mentioned.

These alkaline compounds may be a mixture of two or more.
Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples thereof include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. Is preferred. The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

<Heat curing (firing) treatment>
The color filter after development is preferably subjected to thermosetting treatment. In this case, the thermosetting treatment conditions are such that the temperature is usually 100 ° C. or higher, preferably 150 ° C. or higher, and usually 280 ° C. or lower, preferably 250 ° C. or lower. Selected by range. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

In the case of producing a color filter by an ink jet method, if the colored resin composition of the present invention is photopolymerizable, after the exposure step, if it is thermosetting, after the coating step by the ink jet method, thermosetting Process. Preferred conditions for the thermosetting treatment are the same as described above.
In addition to the manufacturing method described above, the color filter of the present invention applies (1) the colored resin composition of the present invention containing a polyimide resin as a binder resin to a substrate and forms a pixel image by an etching method. It can also be manufactured by the method to do. Also, (2) a method of directly forming a pixel image on a transparent substrate by a printing press using the colored resin composition of the present invention as a colored ink, and (3) using the colored resin composition of the present invention as an electrodeposition liquid. And a method of depositing a colored film on the ITO electrode having a predetermined pattern by immersing the substrate in this electrodeposition solution, and (4) a film coated with the colored resin composition of the present invention is attached to a transparent substrate And a method of forming a pixel image by peeling and image exposure and development, and (5) a method of forming a pixel image with an ink jet printer using the colored resin composition of the present invention as a colored ink.

As a method for producing the color filter, a method suitable for this is employed according to the composition of the colored resin composition of the present invention.
<Formation of transparent electrode>
The color filter of the present invention forms a transparent electrode such as ITO on the image as it is and is used as a part of components such as a color display and a liquid crystal display device. However, the surface smoothness and durability are improved. Therefore, if necessary, a top coat layer such as polyamide or polyimide can be provided on the image. In some cases, the transparent electrode may not be formed in applications such as a planar alignment type driving system (IPS mode).

<Liquid crystal display device (panel)>
Next, the manufacturing method of the liquid crystal display device (panel) of this invention is demonstrated. In the liquid crystal display device of the present invention, an alignment film is usually formed on the color filter of the present invention, spacers are dispersed on the alignment film, and then bonded to the counter substrate to form a liquid crystal cell. Liquid crystal is injected into the cell and connected to the counter electrode to complete. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of decompression in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or higher, preferably 1 × 10 ⁻³ Pa or higher, and usually 1 × 10 ⁻⁷ Pa or lower, preferably 1 × 10 ⁻⁶ Pa or lower. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.

  The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. In the liquid crystal cell into which liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin. The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

<Organic EL display>
When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 4, first, a pattern (pixel 20 or adjacent pixel 20) formed on a transparent support substrate 10 by a colored resin composition. A color filter in which a resin black matrix (not shown) provided between the layers is formed is formed, and an organic light-emitting body 500 is laminated on the color filter with the organic protective layer 30 and the inorganic oxide film 40 interposed therebetween. Thus, an organic EL element can be manufactured. Note that at least one of the pixels 20 is manufactured using the colored resin composition of the present invention.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, published on August 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 thus manufactured, etc. Thus, an organic EL display can be produced. The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited to description of a following example, unless the summary is exceeded.
[1] Synthesis of Compound <Synthesis Example 1: Synthesis of Compound 1>
2,2′-benzidine disulfonic acid (6.88 g, 0.020 mol) was added to water (200 ml) to bring the temperature to 5 ° C., then 35% hydrochloric acid (10.3 g, 0.080 mol), and 23% A sodium nitrate aqueous solution (13.2 g, 0.044 mol) was added and stirred for 30 minutes to obtain a tetrazonium salt. Acetoacetylanilide (7.09 g, 0.040 mol) was dissolved in a methanol / water mixed solution (240 ml / 120 ml), and the above tetrazonium salt solution was added to a solution cooled to 5 ° C. at 20 ° C. to 20% sodium carbonate. While adding the aqueous solution, the solution was kept at pH = 6-8 and added dropwise over 30 minutes. The mixture was further stirred at 5 ° C. for 2 hours. The resulting precipitate was filtered, washed with water, and dried under reduced pressure at 60 ° C. to obtain a sodium salt azo compound (3.8 g, yield 25%).

Water (3800 ml) was added to the azo compound obtained by the above method (3.8 g, 0.0050 mol) and stirred for 1 hour, and then 20% aqueous calcium chloride solution (4.2 g, 0.0080 mol) was added for 3 hours. Stir. The resulting precipitate was filtered, washed with water (700 ml) and dried under reduced pressure at 60 ° C. to obtain the following compound 1 (3.5 g, yield 92%). Compound 1 is dissolved in a mixed solvent of NMP / MeOH and 0.1% HCOOH Water / MeOH = 8/2 is used with an ESI (electro-spray ionization) method using Waters LCT Premier XE. When mass spectrometry was performed, m / z = 71
The peak of 9.1 [Mw- (Ca-H)] was observed, and it was confirmed that the target compound 1 was produced.

<Synthesis Example 2: Synthesis of Compound 2>
The synthesis of Compound 1 was carried out in the same manner as in Synthesis Example 1 except that 5- (acetoacetamido) -2-benzimidazolinone was used as a coupler component instead of acetoacetanilide.
When the obtained compound 2 was subjected to mass spectrometry in the same manner as in Synthesis Example 1, the peak of m / z = 831.1 [Mw- (Ca—H)] was observed to produce the desired compound 2 below. I confirmed that

<Synthesis Example 3: Synthesis of Compound 3>
Synthesis of Compound 1 was performed in the same manner as in Synthesis Example 1 except that p-acetoacetophenetide was used instead of acetoacetanilide as a coupler component. When the obtained compound 3 was subjected to mass spectrometry in the same manner as in Synthesis Example 1, the peak of m / z = 807.2 [Mw- (Ca—H)] was observed to produce the following desired compound 3 I confirmed that

<Synthesis Example 4: Synthesis of Compound 4>
The synthesis of Compound 1 was performed in the same manner as in Synthesis Example 1 except that 4′-chloro-2′-methylacetoacetanilide was used in place of acetoacetanilide as the coupler component. When compound 4 was subjected to mass spectrometry in the same manner as in Synthesis Example 1, the peak of m / z = 817.1 [Mw- (Ca—H)] was observed, and the following desired compound 4 was produced. It was confirmed.

<Synthesis Example 5: Synthesis of Compound 5>
The synthesis of Compound 1 was carried out in the same manner as in Synthesis Example 1 except that 3-methyl-1-phenyl-5-pyrazolone was used as a coupler component instead of acetoacetanilide.

<Synthesis Example 6: Synthesis of Compound 6>
Sodium 6-methyl-2- [4-[[2-oxo-1-[(phenylamino) carbonyl] propyl] azo] phenyl] -7-benzothiazolesulfonate (143 g, 0.27 mol) was added to water (14300 ml). And stirred for 1 hour. Thereafter, 20% aqueous calcium chloride solution (300 g, 0.54 mol) was added and stirred for 3 hours. The resulting precipitate was filtered, washed with water (7000 ml) and dried to obtain the following compound 6 (128 g, yield 90%). When compound 6 was subjected to mass spectrometry in the same manner as in Synthesis Example 1, the peak of m / z = 508.1 [Mw- (Ca—H)] was observed, and the target compound 6 below was produced. It was confirmed.

<Synthesis Example 7: Synthesis of Compound 7>
Instead of sodium 6-methyl-2- [4-[[2-oxo-1-[(phenylamino) carbonyl] propyl] azo] phenyl] -7-benzothiazolesulfonate, 2,2 ′-(triazene-1 , 3-Diyldi-4,1-phenylene) bis (6-methyl-7-benzothiazolesulfonic acid) disodium was used in the same manner as in Synthesis Example 5.

<Synthesis Example 8: Synthesis of Compound 8>
Instead of sodium 6-methyl-2- [4-[[2-oxo-1-[(phenylamino) carbonyl] propyl] azo] phenyl] -7-benzothiazolesulfonate, 3,3 ′-[carbonylbis [ Imino (2-methyl-4,1-phenylene) azo]] bis [1,5-naphthalenedisulfonic acid] tetra-sodium salt was used in the same manner as in Synthesis Example 5 except that tetrasodium was used.

<Synthesis Example 9: Synthesis of Compound 9>
Instead of sodium 6-methyl-2- [4-[[2-oxo-1-[(phenylamino) carbonyl] propyl] azo] phenyl] -7-benzothiazolesulfonate, 3 ′
This was carried out in the same manner as in Synthesis Example 5 except that-[(carbonyldiimino) bis (3-methoxy-4,1-phenylene) bis (azo)] bis [sodium benzenesulfonate] was used.

<Synthesis Example 10: Synthesis of Compound 10>
Instead of sodium 6-methyl-2- [4-[[2-oxo-1-[(phenylamino) carbonyl] propyl] azo] phenyl] -7-benzothiazolesulfonate, 3,3 ′-[carbonylbis ( (Imino-4,1-phenyleneazo)] bis [6-hydroxybenzoic acid] disodium was used in the same manner as in Synthesis Example 5.

＜合成例１１：化合物１２の合成＞
合成例１にて２，２’−ベンジジンジスルホン酸の代わりにデヒドロチオ−ｐ−トルイジンスルホン酸を、アセト酢酸アニリドの代わりに５−（アセトアセトアミド） −２−
ベンズイミダゾリノンを用いた以外同様に行い、化合物１１を得た。

<Synthesis Example 11: Synthesis of Compound 12>
In Synthesis Example 1, dehydrothio-p-toluidinesulfonic acid was used instead of 2,2′-benzidinedisulfonic acid, and 5- (acetoacetamido) -2-
Compound 11 was obtained in the same manner except that benzimidazolinone was used.

<Synthesis Example 12: Synthesis of Compound 12>
In Synthesis Example 1, dehydrothio-p-toluidinesulfonic acid was used instead of 2,2′-benzidinedisulfonic acid, and 3-methyl-1-phenyl-5-pyrazolone was used instead of acetoacetic acid anilide. Compound 12 was obtained.

<Reference Synthesis Example 1: Synthesis of Pigment Derivative 1>
PR254 (100 g) was added to 25% fuming sulfuric acid (900 g) and reacted at 50 ° C. for 4 hours. After cooling, the reaction mixture was precipitated in ice water (10000 ml), the precipitate was filtered and washed with water, dried, suspended in water, added with aqueous ammonia until PH = 7, and then crystallized with isopropyl alcohol. Filtration and washing were performed to obtain a water paste. This water paste was dried to obtain a diketopyrrolopyrrole derivative having an ammonium sulfonate group introduced therein, that is, pigment derivative 1 (70 g). The introduction of sulfo group was 0.8 to 1 on average per molecule.

<Synthesis Example 13: Synthesis of Resin S (corresponding to (D-1-3) Copolymer)>
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2.2'-azobis-2-methyl 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 8400, acid value of 80 mgKOH / g.

[2] Preparation of Pigment Dispersion <Example 1: Preparation of Red Pigment Dispersion (1) Using Compound 1>
4.4 parts by weight of the compound 1 obtained in Synthesis Example 1 as a lake dye (ie, component (B)), 5.2 parts by weight of the pigment derivative obtained in Synthesis Example 11 as a pigment derivative, and fine particles as a pigment C. I. 100 parts by weight of Pigment Red 254, 34.1 parts by weight of the resin S obtained in Synthesis Example 12, and “BYK-LPN691” manufactured by BYK Chemie as a dispersant.
9 ”(corresponding to (C-2) dispersant) and 669 parts by weight of propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as“ PGMEA ”) as a solvent. 1793 parts by weight of beads were added and dispersed for 8 hours with a paint shaker to prepare a red pigment dispersion (1).

<Dispersant “BYK-LPN6919” (by Big Chemie)>
It is a methacrylic acid AB block copolymer, the amine value is 121 mgKOH / g, and the acid value is 1 mgKOH / g or less.
Of the repeating units having a nitrogen atom-containing functional group contained in the B block, about 100 mol% has a structure represented by the following formula (i), and the repeating unit represented by the following formula (ii) The ratio in one molecule in terms of the monomer composing the acid block copolymer was 7.5 mol%.

<Examples 2 to 10: Preparation of red pigment dispersions (2) to (10) using compounds 2 to 10, respectively>
Preparation was performed in the same manner as in Example 1 except that the compounds 2 to 10 obtained in Synthesis Examples 2 to 10 were used as lakeing dyes.
<Example 11: Preparation of red pigment dispersion (11) using compound 6>
The same preparation as in Example 1 was performed except that 9.6 parts by weight of the compound 6 obtained in Synthesis Example 6 was used as a lake dye without using the pigment derivative obtained in Synthesis Example 11.

<Examples 12 and 13: Preparation of red pigment dispersions (12) and (13) using compounds 7 and 10, respectively>
Preparation was carried out in the same manner as in Example 11 except that Compound 7 and Compound 10 were used as lake dyes.
<Comparative Example 1: Preparation of red pigment dispersion (14)>
The same preparation as in Example 1 was carried out except that the compound 1 obtained in Synthesis Example 1 and the pigment derivative 1 obtained in Reference Synthesis Example 1 were not used. I couldn't.

<Comparative Example 2: Preparation of red pigment dispersion (15)>
Preparation was carried out in the same manner as in Example 1 except that Compound 1 obtained in Synthesis Example 1 was not used and 9.6 parts by weight of the pigment derivative obtained in Synthesis Example 11 was used.
[3] Preparation of Colored Resin Composition Subsequently, the various red pigment dispersions (1) to (15) obtained in [2] above were mixed with the components described in Table 1 below, and various colored resin compositions were prepared. A product was prepared.

[4] Preparation of colored resin film and colored plate Each of the colored resin compositions obtained in [3] above was spin-coated on a transparent glass substrate ("AN-100" manufactured by Asahi Glass Co., Ltd.) at 80 ° C. Was pre-baked on a hot plate for 3 minutes to obtain a dried coating film.
Subsequently, the obtained dried coating film was exposed at 60 mJ / cm ² with a high-pressure mercury lamp, and then post-baked in an oven at 230 ° C. for 30 minutes to prepare various colored resin films.

In the application, after the post-baking, the rotational speed was adjusted so that the color coordinates of the obtained dry coating film became y = 0.648.
The thickness of the obtained colored resin film was about 2.4 μm. Thus, various colored plates having a colored resin film on a transparent glass substrate were produced.
[5] Measurement of luminance (Y value) Using the spectrophotometer (Hitachi High-Technologies spectrophotometer "U-3010") for the various colored plates obtained in [4] above, the chromaticity with a C light source ( Y, x, y) were measured. The results of Y value are shown in Table 2.

[6] Measurement of contrast FIGS. 2A and 2B are schematic diagrams for explaining a method of measuring the chromaticity of parallel transmitted light and orthogonal transmitted light of a colored plate.
First, as shown in FIG. 2A, polarizing plates 33 and 35 are stacked on both sides of the obtained colored plate (hereinafter sometimes referred to as “colored plate 34”), and With the polarization axes parallel to each other, the light L of the backlight 37 is applied from the side of one polarizing plate 35 and the light Lp (the luminance of the parallel transmitted light) transmitted through the other polarizing plate 33 is the color luminance. The measurement was performed under the condition of 2 ° visual field using “BM-5A” 32 manufactured by Topcon Techno House.

Next, as shown in FIG. 2B, in a state where the polarization axes of the polarizing plates 33 and 35 are orthogonal to each other, the light 36 of the backlight 37 is applied from one polarizing plate 35 side, and the other polarizing plate 33 is applied. The luminance Lc (the luminance of the orthogonal transmitted light) transmitted through the light was measured with the color luminance meter 32 in the same manner as the above Lp.
The backlight 37 has an emission spectrum as shown in FIG. This spectrum was measured and calculated using a Konica Minolta spectral radiance meter CS-1000A and a filter “ND filter ND4” manufactured by Kenko in order to control the amount of light and facilitate the measurement.

The polarizing plates 33 and 35 have the spectral characteristics shown in FIG.
The contrast of the various colored plates was calculated from the brightness Lp of the parallel transmitted light and the brightness Lc of the orthogonal transmitted light using the formula Lp / Lc. In addition, the blank value when measured using raw glass instead of various colored plates was 12000. The measurement results are shown in Table 2.
[7] Evaluation on generation of foreign matter after firing The surface of each colored plate obtained in [4] above is visually observed at a magnification of 50 times using an optical microscope, and the colored substrate surface is observed within a range of 1 cm × 1 cm. When observed, there is almost no pigment-derived crystal (0 to 10%), ◯ is slightly observed (10 to 20%), and a large amount is observed (20% to) ×. did. The results are shown in Table 2.

[8] Preparation of atomized pigment <Example 14: Preparation of red atomized pigment (R-1) using compound 1>
Compound 1 (3.0 parts by weight) obtained in Synthesis Example 1 as an atomization aid, C.I. I. Pigment Red 254 (50 parts by weight), sodium chloride (550 parts by weight), diethylene glycol (110 parts by weight), and resin S obtained in Synthesis Example 13 (15 parts by weight in solid content) were charged into a double-arm kneader. Atomization was performed by a solvent salt milling method at 50 ° C. for 4 hours. This kneaded product is put into 7000 parts by weight of water, stirred for 30 minutes, filtered and washed with water, after removing sodium chloride and diethylene glycol, dried and pulverized at 50 ° C. to obtain a red atomized pigment (R-1). Obtained.
[9] Preparation of pigment dispersion <Preparation of red pigment dispersion (R-1) using red atomized pigment (R-1) containing compound 1>
9.6 parts by weight of the compound 2 obtained in Synthesis Example 2 as a dispersion aid and finely atomized C.I. obtained in Example 14 as a pigment. I. 100 parts by weight of Pigment Red 254, 34.1 parts by weight of the resin S obtained in Synthesis Example 13, and “BYK-LPN6919” (manufactured by BYK Chemie) (D-2) as a dispersant. 38.6 parts by weight) and 669 parts by weight of PGMEA as a solvent were stirred and mixed, 400 parts by weight of zirconia beads were added, and the mixture was dispersed for 6 hours by a bead mill to prepare a red pigment dispersion (R-1).
The red pigment dispersion (R-1) was prepared, and it was visually confirmed that the dispersion after 1 hour had fluidity.
<Examples 15 to 17: Red pigment dispersions (R-2) to (R-4) using red atomized pigments (R-2) to (R-4) each containing compounds 6, 11 and 12 Preparation>
In the preparation of [8] atomization pigment of Example 14, Compound 1 obtained in Synthesis Example 1 used as an atomization aid was replaced with Compounds 6, 11 and 12 obtained in Synthesis Examples 6, 11 and 12, respectively. The pigment dispersion was prepared in the same manner as in Example 14 except that the red atomized pigments (R-2) to (R-4) were obtained by changing the red pigment dispersion (R-2). To (R-4) were prepared.
<Comparative Example 3: Preparation of red pigment dispersion (R-5) using red atomized pigment (R-5) containing pigment derivative 1>
In the preparation of [8] atomized pigment of Example 14, the compound 1 obtained in Synthesis Example 1 used as an atomization aid was changed to the pigment derivative 1 obtained in Reference Synthesis Example 1, and red atomized. A pigment dispersion was prepared in the same manner as in Example 14 except that the pigment (R-5) was obtained, thereby preparing a red pigment dispersion (R-5).
[10] Preparation of colored resin composition Subsequently, the red pigment dispersions (R-1) to (R-5) obtained in [9] above were mixed with the components described in Table 1 above, and various types were prepared. A colored resin composition was prepared.
[11] Preparation of colored resin film and colored plate Using the colored resin composition obtained in [10] above, a colored plate was prepared by the method of [4].
[12] Measurement of luminance (Y value) The color plate obtained in the above [11] is measured using a spectrophotometer “U-3310” (manufactured by Hitachi High-Technologies Corporation) for chromaticity (Y, x, y) was measured.
The results obtained are shown in Table 3.

  As shown in Table 3, it can be seen that the pixel formed using the colored resin composition containing the additive of the present invention has high luminance and hardly shows any crystalline foreign matter after firing.

DESCRIPTION OF SYMBOLS 10 Transparent support substrate 20 Pixel 30 Organic protective layer 32 Color luminance meter 33, 35 Polarizing plate 34 Colored plate 36 Light 37 Backlight 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection Layer 55 Cathode 100 Organic EL element 500 Organic light emitter

Claims (10)

(A) a pigment, and (B) an alkaline earth metal salt of a water-soluble dye having an acidic group ,
The (B) alkaline earth metal salt of a water-soluble dye having an acidic group contains a compound represented by the following general formula (1) or a compound represented by the general formula (2) Dispersion.

(R ¹¹ and R ¹² in the general formula (1) are each independently an aromatic group which may have a substituent, or a structure represented by the following general formula (3) or the general formula (4). The structure represented by is shown.
R ²¹ in the general formula (2) represents a 5- or 6-membered heterocyclic group containing one or more nitrogen atoms.
R ²² in the general formula (2) is an aromatic group which may have a substituent, a structure represented by the following general formula (3), a structure represented by the following general formula (4), or the following general formula The structure represented by Formula (5) is shown.
n represents 0 or 1.

(In the above general formulas (3) and (4), R ¹ , R ² , R ³ and R ⁴ each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Represents an optionally substituted alkoxy group or an optionally substituted aromatic group, and * represents a site bonded to the azo group in the general formula (1) or (2).
R ⁵ in the general formula (5) has the same meaning as R ¹ and R ^{2 in} the general formula (3) and R ³ and R ⁴ in the general formula (4) . * Shows the site | part couple | bonded with the azo group in General formula (2). )
X in the general formula (1) represents a direct bond or any linking group represented by the following structural formulas (1-1) to (1-11).

(Note that * in the above structural formulas (1-1) to (1-11) represents a site bonded to the benzene ring in the general formula (1).
R ¹¹¹ in the structural formula (1-3) is a hydrogen atom, a hydroxyl group, or —NA ¹ A ² (A ¹ and A ² are each independently a hydrogen atom or an alkyl group which may have a substituent. Represents an alkoxy group which may have a substituent, or an aromatic group which may have a substituent. )
Z in the general formula (2) is a direct bond or any structure represented by the following structural formulas (2-11) to (2-13) (note that the following structural formula (2-11) ) To (2-13) indicate a site that binds to the benzene ring and R ²¹ in the general formula (2) .

In addition, the benzene ring in the general formulas (1) and (2) further includes a nitro group, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a sulfo group. At least one substituent selected from the group consisting of a sulfonate group, a carboxy group, a carboxylate group, a phospho group, a phosphate group, and an optionally substituted aromatic group You may have.
Furthermore, R ¹¹ and R ^{12 in} the general formula (1), R ²² in the general formula (2) , R ¹¹¹ in the structural formula (1-3 ), and the benzene ring in the general formula (1) or (2) At least one of the substituents bonded to is an alkaline earth metal salt group having an acidic group or a group having an alkaline earth metal salt group having an acidic group. )   (A) The pigment is C.I. I. (Color Index) selected from the group consisting of Pigment Red 177, Pigment Red 242, Pigment Red 254, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 150, Pigment Yellow 180, Pigment Green 7, Pigment Green 36, and Pigment Green 58 The pigment dispersion according to claim 1, further comprising at least one pigment.   (B) The content of the alkaline earth metal salt of the water-soluble dye having an acidic group is 0.01 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the pigment (A). Item 3. A pigment dispersion according to Item 1 or 2. Furthermore, (C) A dispersing agent is contained, The pigment dispersion liquid of any one of Claims 1-3 characterized by the above-mentioned. A colored resin composition for a color filter, comprising the pigment dispersion according to any one of claims 1 to 4 and (D) a binder resin. The colored resin composition for a color filter according to claim 5 , further comprising (E) a polymerizable monomer. Furthermore (F) a photopolymerization initiator及 beauty / or color resin composition for color filters of claim 5 or 6, characterized in that it contains a thermal polymerization initiator. A color filter comprising a pixel produced using the colored resin composition for a color filter according to claim 5 . A liquid crystal display device comprising the color filter according to claim 8 . An organic EL display comprising the color filter according to claim 8 .

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