JP2013035917A - Pigment dispersion, colored resin composition, color filter, liquid crystal display device and organic el display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment dispersion and a colored resin composition, suppressing yield reduction due to agglomerated foreign matter or thickening in production process of a color filter, and small in temporal thickening of viscosity.SOLUTION: This pigment dispersion includes (A) yellow pigment, (B) a solvent and (C) a dispersant, in which the dispersant contains a polymer which has a primary to tertiary amino group and/or quaternary ammonium group on the side chain; and the content ratio of a monomer having the primary to tertiary amino group and/or quaternary ammonium group is 20 mol% or more in the monomer composition constituting the polymer, and the amount of water in the pigment dispersion is 0.4-1.8 wt.%.

Description

  The present invention resides in a pigment dispersion, a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

Pixels, black matrixes, photo spacers, rib materials, overcoats, etc. used in the manufacture of display members such as liquid crystal display devices are generally applied to substrates with curable compositions for various applications. Various images are formed through the forming process.
Conventionally, spin coating has been used in the coating process, but in recent years, there has been a shift to the slit-and-spin method and the die coating method because of the need for larger substrates and reduced liquids.

However, in the slit-and-spin method and the die coating method, there is a serious problem that the aggregated foreign matter generated by drying at the tip of the dispensing nozzle becomes a peeled-off foreign matter on the coating film, thereby reducing the yield.
In order to solve this problem, for example, in Patent Document 1, a dry film formed with a colored image forming photosensitive solution is immersed in a solvent and dissolved within 5 minutes (hereinafter, this method is referred to as “re-dissolution” A property satisfying this is sometimes referred to as “re-solubility.”) A colored image forming photosensitive solution and its method are disclosed.

  Patent Document 2 discloses a device for cleaning the nozzle tip.

JP 2002-23352 A JP-A-9-192666

However, in Patent Document 1, since the aggregated foreign matter once generated in the actual manufacturing process is dispersed on the coating surface without waiting for the re-dissolution time, the color reproducibility is low and the yield due to the aggregated foreign matter is reduced. There was a problem that it was insufficient as an improvement.
Further, in Patent Document 2, it is difficult to completely remove the foreign matter at the sharp tip of the nozzle in the actual manufacturing process, and it is necessary to interrupt the coating operation for cleaning the nozzle. There was a problem of inhibiting. Further, if the cleaning is not complete, a remaining liquid pool is generated at the tip of the nozzle, so that there is a problem that nonuniformity (unevenness) of the coating is caused.

In view of the above problems, the present invention is a yield in the color filter manufacturing process due to aggregated foreign matters and thickening, particularly when a resin containing a large amount of primary to tertiary amino groups and / or quaternary ammonium groups is used as a dispersant. It is an object of the present invention to provide a pigment dispersion and a colored resin composition that suppress the decrease, that is, have high re-solubility and low viscosity increase with time.
Another object of the present invention is to provide a color filter having good color reproducibility, a high-quality liquid crystal display device, and an organic EL display device.

As a result of intensive studies, the present inventors have found that yellow pigments and primary to tertiary amino groups and / or 4
In the case where a resin having a large amount of a quaternary ammonium group is contained as a dispersant, the inventors have found that the above problem can be solved by adjusting the amount of water in the pigment dispersion, and have reached the present invention.
That is, the present invention relates to a pigment dispersion containing (A) a yellow pigment, (B) a solvent and (D) a dispersant, and the (D) dispersant contains a polymer. A monomer having a tertiary amino group and / or quaternary ammonium group in the side chain, and the content ratio of the monomer having the primary to tertiary amino group and / or quaternary ammonium group constituting the polymer The composition is 20 mol% or more, and the water content in the pigment dispersion is 0.4 wt% or more and 1.8 wt% or less. It exists in a filter, a liquid crystal display device, and an organic EL display device.

The pigment dispersion and colored resin composition of the present invention have good re-solubility and a small increase in viscosity over time. For this reason, in the color filter manufacturing process, it is possible to suppress a decrease in yield in the color filter manufacturing process due to an increase in aggregated foreign matter and viscosity over time.
Further, the obtained color filter has good color reproducibility, and the liquid crystal display device and the organic EL display device are of high quality.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present invention.

Embodiments of the present invention will be described in detail below, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present invention, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” "Means" acrylic acid and / or methacrylic acid ".

“Total solid content” means all components of the pigment dispersion or colored resin composition of the present invention other than the solvent components described later.
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 weight of the base and the equivalent amount of KOH per 1 g of the solid content of the dispersant. The measuring method will be described later.

Terms such as “CI Pigment Green” mean the color index (CI).
Furthermore, the “coloring material” in the present invention is a general term for “pigment” and “dye”.
The pigment dispersion of the present invention comprises (A) a yellow pigment, (B) a solvent and (D) a pigment dispersion containing a dispersant, and (D) a polymer as the dispersant. To a tertiary amino group and / or quaternary ammonium group in the side chain, and the content ratio of the monomer having the primary to tertiary amino group and / or quaternary ammonium group is a single component constituting the polymer. The pigment dispersion is characterized in that it contains 20 mol% or more in the monomer composition, and the water content in the pigment dispersion is 0.4 wt% or more and 1.8 wt% or less.
First, (D) the dispersant will be described.

[(D) Dispersant]
The pigment dispersion of the present invention contains (D) a polymer as a dispersant, and the polymer has a primary to tertiary amino group and / or a quaternary ammonium group in the side chain, In the monomer composition constituting the polymer, the content ratio of the monomer having an amino group and / or a quaternary ammonium group is 2
It is a polymer of 0 mol% or more (hereinafter sometimes referred to as “specific polymer”).
The content ratio of the monomer having a primary to tertiary amino group and / or a quaternary ammonium group is usually 20 mol% or more, preferably 25 mol% or more, based on the entire copolymerization monomer constituting the polymer. Preferably it is 30 mol%.

The copolymer is preferably a block copolymer containing a repeating unit having solvophilicity and a repeating unit having a primary to tertiary amino group and / or a quaternary ammonium group in the side chain.
Of these, (meth) acrylic block copolymers are preferred.
First, the repeating unit having a primary to tertiary amino group in the side chain in the (meth) acrylic block copolymer will be described.

(Repeating unit having a primary to tertiary amino group in the side chain)
The primary to tertiary amino group is preferably —NR ⁴¹ R ⁴² (wherein R ⁴¹ and R ⁴² each independently represents a hydrogen atom or a cyclic or chain-like alkyl group which may have a substituent). Represents an aryl group which may have a substituent, or an aralkyl group which may have a substituent.), And a partial structure (repeating unit) containing this is represented by the following formula, for example. Is done.

(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 formula is particularly preferably used.

(Wherein R ⁴⁴ has the same meaning as described above.)
(Repeating unit having a quaternary ammonium group in the side chain)
As a repeating unit having a quaternary ammonium group, the quaternary ammonium group may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group. Moreover, as such a quaternary ammonium group, what contains the partial structure represented by following formula (VI) especially is preferable.

In the above formula (VI), R ³⁴ represents a hydrogen atom or a methyl group.
X ¹ represents a divalent linking group.
R ^{31 to} R ³³ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon ring 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 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), and the like, preferably —COO—R ³⁶ —.
Examples of the counter anion M ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

(Repeating unit having solvophilicity)
On the other hand, the repeating unit having solvophilicity constituting the block copolymer of the dispersant does not have a primary to tertiary amino group and a quaternary ammonium group, and the above-described primary to tertiary amino groups and quaternary ammonium are used. If it consists of a monomer copolymerizable with the monomer which has group, there will be no restriction | limiting in particular.

Examples of the copolymerizable monomer constituting the solvophilic property include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, and (meth) acrylic. Isopropyl acid, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, (Meth) acrylate monomers such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; vinyl acetate monomers; Ethers include comonomers such glycidyl ether monomers such as crotonic acid glycidyl ether.

Among these, polyalkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate are preferable.
Among these partial structures derived from copolymerization monomers, a partial structure represented by the following formula (VII) is particularly preferable.

(In the formula (VII), n represents an integer of 1 to 5, but when there are a plurality of the units, that is, the formula (VII) 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 above formula (VII) is usually 5% by weight or more, preferably 7% by weight or more and usually 40% by weight or less based on the entire copolymerization monomer constituting the polymer.

Within the above range, the affinity with the dispersion solvent is improved, and the stability of the dispersion system is increased, which is preferable.
In synthesizing such a (meth) acrylic block copolymer, JP-A-60-89452, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12 , 79 (1984), BC Anderson, GD Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), K. Hatada, K Ute, et al, Polym. J.18, 1037 (1986), Koichi Right-hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46, 189 ( 1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al. , Macromolecules, 20, 1473 (1987), K. Matyaszewski et al, Chem. Rev. 2001, 101, 2921-2990, etc., can be used.

When the AB block copolymer and the ABA block copolymer according to the present invention are polymers having a primary to tertiary amino group in the side chain, the amine value in 1 g of the solid content is preferably 90 mgKOH / g or more, More preferably, it is 100 mgKOH / g or more, More preferably, it is 150 mgKOH / g or less, More preferably, it is 140 mgKOH / g or less.
Within the above range, it is preferable in that the adsorptive power to the pigment surface is sufficient and the dispersion stability is good.

The amine value of the dispersant (in terms of effective solid content) 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 [mg KOH / g] = (5.61 × 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.)
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 50 mgKOH / g or less, preferably 40 mgKOH / g or less. Preferably it is 30 mgKOH / g or less.
In the present invention, a commercially available (meth) acrylic block copolymer having the same structure as described above can also be applied.

(Acid value)
The acid value of the specific polymer in the present invention 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, it is 40 mgKOH / g or less, Most preferably, it is 30 mgKOH / g or less.

(Molecular weight)
The molecular weight of the specific polymer in the present invention is usually 1000 or more and usually 100,000 or less in terms of polystyrene-reduced 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.
When the average primary particle size of the pigment is small, the specific surface area increases, so that the amount of dispersant adsorbed per unit area decreases. In such a case, the above-described dispersant composed of the AB block copolymer or ABA block copolymer is particularly preferably used because the difference in the effect is very remarkable as compared with the dispersant having another structure. Is.

(Content)
The (D) dispersant in the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and preferably 200% by weight or less, more preferably 100% by weight, based on the total amount of pigment in the pigment dispersion. It is as follows.

Furthermore, content of the specific polymer in this invention is 10 weight% or more normally in all the (D) dispersing agents, Preferably it is 30 weight% or more. Since it is particularly preferable to use only a specific polymer as the dispersant, the upper limit is ideally 100% by weight.
Furthermore, the content of the (D) dispersant with respect to the (A) yellow pigment described later is usually 10% by weight or more, and usually 100% by weight or less, preferably 50% by weight or less, more preferably 40% by weight or less.

Within the above range, the colored resin composition to be described later is preferably good in alkali developability and is less likely to be peel development. In addition, since a necessary and sufficient amount of the dispersant is adsorbed on the pigment surface, the aggregation of the pigment can be effectively prevented, and high dispersion stability can be ensured.
The (D) dispersant in the present invention may contain only one kind of polymer having a primary to tertiary amino group and / or a quaternary ammonium group in the side chain, and contains two or more different kinds. You may do it.

(D) By controlling the content of the dispersant within the above range, a necessary and sufficient amount of the dispersant adheres to the pigment surface, so that aggregation can be effectively prevented and the viscosity or gel is increased. Therefore, high dispersion stability can be ensured.
The pigment dispersion and colored resin composition of the present invention may contain a dispersant other than the specific polymer described above as long as the effects of the present invention are not impaired.

<Other dispersants>
The other dispersant is not particularly limited as long as the effects of the present invention are not impaired. For example, the following (D-1) dispersant (hereinafter, referred to as “(D-1) dispersant” may be used. ).
(D-1) 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 (D-1) dispersant include EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol) ), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), etc.

[(A) Yellow pigment]
The pigment dispersion and colored resin composition of the present invention contain (A) a yellow pigment.
(A) Examples of yellow pigments include monoazo, diazo, condensed diazo, benzimidazolone, azo metal complexes, azomethine, pyrazolone, quinophthalone, isoindoline, isoindolinone, and flavatron. Of these, azo, quinophthalone, and isoindoline are preferable because they are excellent in transparency and contrast.

Furthermore, although the preferable specific example as (A) yellow pigment is shown below, this invention is not limited to these.
(Specific examples of yellow pigment)
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 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, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127: 1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 70,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191: 1,192,193,194,195,196,197
198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and a 1: 1 complex of azobarbituric acid represented by the following formula (II) with nickel or a compatible isomer thereof: Examples include compounds in which other compounds are inserted (hereinafter referred to as “nickel azo complexes represented by the formula (II)”).

  Examples of the other compound include a compound represented by the following formula (II-1).

Of these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and a nickel azo complex represented by the formula (II), more preferably C.I. I. Pigment Yellow 83, 138, 139, 180, and the nickel azo complex represented by the formula (II).
In particular, since the nickel azo complex represented by the formula (II) contains a large number of carbonyl groups, the water molecules are hydrogen-bonded here, so that aggregation of the pigment is suppressed and the effect of the present invention can be easily obtained. Guessed.

That is, in the present invention, a pigment having a group (such as a hydroxyl group or a carbonyl group) capable of hydrogen bonding with water molecules is presumed to have a great effect.
In addition, the average primary particle size of the (A) yellow pigment in 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 (A) yellow pigment to be used within the above range, the depolarization characteristics are kept good, high contrast, transmittance, etc. are realized, dispersion stability is good, heat resistance and A pigment dispersion and a colored resin composition having excellent light resistance 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 yellow pigment (A) thus obtained may be used alone, but may be used alone or in combination of two or more kinds within the range not impairing the effects of the present invention.
The pigment dispersion of the present invention may contain other pigments.

(Other pigments)
As other pigments, pigments of various colors such as a red pigment, a green pigment, a purple pigment, an orange pigment, and a brown pigment can be used.
Examples of the chemical structure of various pigments include organic pigments such as azo, 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, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. 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 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 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. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  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.

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 the pigment dispersion and colored resin composition of the present invention, red pigments and green pigments are preferred as pigments used in combination for chromaticity adjustment. Specific examples of the red pigment and the green pigment that are preferable for use in combination are as described above.

(Pigment content)
The content of (A) yellow pigment in all pigments contained in the pigment dispersion and colored resin composition of the present invention is usually 0.05% by weight or more, preferably 0.08% by weight or more, more preferably 0. .1% by weight or more, and usually 100% by weight or less.
Within the above range, it is preferable in that the effect of the present invention can be obtained satisfactorily.

The total pigment content in the pigment dispersion of 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, based on the total solid content. % Or more, preferably 0.5% by weight or more, more preferably 1% by weight or more.
The total content of the pigment in the colored resin composition of the present invention is usually 3% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 50% by weight or less, preferably 40% by weight. Hereinafter, it is more preferably 30% by weight or less.

[(B) Solvent]
The (B) solvent used in the present invention is not particularly limited as long as it has a function of satisfactorily dissolving or dispersing (A) a yellow pigment, (D) a dispersant, and other components to be mixed in some cases. Although there are no, examples of the solvent include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Mono- or polyhydric alcohols (alcohol solvents) such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, butyl cellosolve;

aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;

Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
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, butyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names). These solvents may be used alone or in combination of two or more.

The pigment dispersion and colored resin composition of the present invention preferably contain an alcohol-based solvent, and particularly preferably contains butyl cellosolve, from the viewpoint of high dispersion stability in the solvent.
In the pigment dispersion of the present invention, the alcohol solvent is usually 10% by weight or more, preferably 20% by weight, and usually 40% by weight or less, preferably 30% by weight or less.
Further, the content of the solvent in the pigment dispersion of the present application is not particularly limited, but is usually 99% by weight or less, usually 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more. .

Further, the content of the solvent in the colored resin composition of the present invention is not particularly limited, but is usually 99% by weight or less, usually 75% by weight or more, preferably 80% by weight or more, more preferably 82% by weight or more. It is.
It is preferable that it is in the above-mentioned range in terms of viscosity suitable for coating at an appropriate concentration for forming a coating film.

[Moisture content of pigment dispersion]
The water content of the pigment dispersion of the present invention is usually 0.4% by weight or more, preferably 0.6% by weight or more, more preferably 0, as measured by the following (Method for measuring the water content of the pigment dispersion). 0.7% or more, usually 1.8% or less, preferably 1.6% or less, and more preferably 1.3% or less.
Within the above range, it is preferable in that the effect of the present invention can be obtained satisfactorily.
The water added to bring the water content within the above range is not particularly limited as long as the effects of the present invention are not impaired. For example, in addition to ultrapure water, clean water, distilled water, and ion-exchanged water may be used. Can be mentioned.

(Measurement method of water content of pigment dispersion)
In the present invention, the water content of the pigment dispersion is measured by the Karl Fischer method under the following conditions.
・ Device: Karl Fischer moisture meter KF-100 (Mitsubishi Chemical Analytech)
・ Injection volume: 1 mL
-Titration solvent: Aquamicron titrant SS-Z 3mg
Titer 2.5~3.5mgH ₂ O / ml
・ Dehydrated solvent: Aquamicron dehydrated solvent GEX
The measuring device for specifying the present invention is not particularly limited as long as the same measurement as that of the above apparatus is possible, but it is preferable to use the above apparatus.

<Reason for effect>
By setting it as the structure of this invention, it estimates as follows about the reason which the resolvability with respect to a solvent becomes favorable.
The specific polymer has a primary to tertiary amino group and / or a quaternary ammonium group in the side chain and has a high content ratio.

Therefore, if there is no compound having polarity in the vicinity, for example, a polar solvent, the polymer tends to aggregate due to the amino group or ammonium group in the side chain.
If water is present as a polar solvent, the polymer is less likely to aggregate, and the amino groups and ammonium groups in the side chains are more easily adsorbed to the pigment.
In addition, when a large amount of water is contained as a polar solvent, a binder resin described later aggregates and the viscosity of the pigment dispersion tends to increase.
From this, the re-solubility with respect to a solvent becomes favorable by making the moisture content into the range of this invention in the pigment dispersion liquid containing a specific polymer.

[Method for preparing pigment dispersion]
Various methods can be adopted as a method for producing the pigment dispersion of the present invention, and an example thereof is shown below.
First, (A) a yellow pigment, (B) a solvent, and (D) a dispersant are respectively weighed in predetermined amounts, and in the dispersion treatment step, the pigment is dispersed to obtain a liquid 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 into fine particles, so that the colored resin composition using the pigment dispersion of the present invention has improved coating properties and the transmittance of the product color filter substrate.

  When the pigment is dispersed, a binder resin described later or a dispersion aid may be used in combination as appropriate. For example, 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 pigment dispersion (pigment, solvent, dispersant, etc.) and the size of the sand grinder apparatus.

In addition, what is necessary is just to adjust using various means in order to make the moisture content of a pigment dispersion liquid into the said range.
Specifically, the water content of the pigment dispersion may be appropriately measured while adding water to the pigment dispersion, and prepared so as to be within the scope of the present invention.
Water may be added before the dispersion treatment step or after the dispersion treatment.
When added before the dispersion treatment step, the order of mixing is not particularly limited.
Further, when water is excessively added, dehydration may be performed using various means.

The timing of dehydration is not particularly limited, and when water addition is performed before the dispersion treatment, the dehydration may be continued or may be dehydrated after the dispersion treatment.
Examples of the dehydration means include a method using a porous material such as molecular sieve, or a dehydrating agent such as sodium sulfite (Na ₂ SO ₃ ) or calcium chloride. In this case, these porous materials and dehydrating agents are added to each component before mixing and the pigment dispersion after mixing, mixed by a technique such as stirring, and after dehydration, the porous materials and dehydrating agents are filtered. Or the like.

  The detailed conditions of dehydration are not particularly limited, and may be adjusted as appropriate according to the dehydration technique and dehydration timing. For example, when a molecular sieve is mixed with the mixed pigment dispersion to perform dehydration, Molecular Sieves 3A 1/16 (manufactured by Wako Pure Chemical Industries, Ltd.) can be used as the molecular sieve.

[Dispersion aid]
The pigment dispersion or colored resin composition of the present invention may contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

The content of the dispersion aid in the pigment dispersion and colored resin composition of the present invention is usually 0.1% by weight or more, usually 30% by weight or less, based on the total pigment including (A) the yellow pigment, Preferably it is 20 weight% or less, More preferably, it is 10 weight% or less, More preferably, it is 5 weight% or less.
Within the above range, the effect as a dispersion aid is effectively obtained, and this is preferable in terms of good dispersibility and dispersion stability.

[Dispersion resin]
The pigment dispersion and colored resin composition of the present invention may contain a part or all of a resin selected from (C) binder resin or other binder resin described later as the following dispersion resin.
Specifically, in the dispersion treatment step to be described later, the (C) binder resin is added to the (D) dispersant by adding the (C) binder resin together with the components such as the (D) 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 (D) dispersant added can 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.

Thus, 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 (C) binder resins described later can be used.
The acid value of the dispersion resin is preferably 0.5 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 150 mgKOH / g. The following are 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 the pigment dispersion and (C) a binder resin. Further, if necessary, other components may be contained, and it is preferable to contain (E) a polymerizable monomer, (F) a photopolymerization initiation system and / or a thermal polymerization initiation system, etc. as other components.

[(C) Binder resin]
(C) The preferred resin for the binder resin differs depending on the curing means.
When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (C) binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, 11-14144, JP-A No. 11-174224, JP-A No. 2000-56118, JP-A No. 2003-233179, and the like can be used. C-1) to (C-5) resins and the like.

  (C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or an alkali-soluble resin (hereinafter referred to as “resin (C-1)”) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .)

(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”)
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as “resin (C-3)”).
(C-4): (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)

(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
Of these, the resin (C-1) is particularly preferable, and the resin will be described below.
The resins (C-2) to (C-5) may be any ones that are dissolved in an alkaline developer and have solubility to the extent that the desired development processing is performed. This is the same as that described as the same item in Japanese Patent No. 025813. The preferred embodiment is also the same.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.

  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 (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (7) Acrylate is preferred.
The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (7) contains 5 to 90 mol% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

In the above formula (7), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (8).

The formula ^{(8), R} 91 ~R ⁹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among these, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b), or (8c) are particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by the said Formula (8) may be used individually by 1 type, and may use 2 or more types together.
As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (8), the heat resistance and strength excellent in the colored resin composition can be improved. , Styrene, (meth) acrylic acid-n-butyl, (meth) acrylic acid-tert-butyl,
(Meth) acrylic acid cyclohexyl, (meth) acrylic acid isobornyl, (meth) acrylic acid adamantyl, (meth) acrylic acid benzyl, (meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide, Can be mentioned.

The content ratio of repeating units derived from at least one selected from the above monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer.
In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and strength are sufficient, which is preferable.
The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as an unsaturated monobasic acid added to an epoxy group, 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 may be used alone or in combination of two or more.

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. It is preferable for it to be in the above range since the colored resin composition is excellent in stability over time. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%.

Within the above range, the remaining film ratio and solubility during development are sufficient, which is preferable.
In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to this hydroxyl group.
Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

  The polystyrene-reduced weight average molecular weight (Mw) of the above-described binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. 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.

In addition, the acid value of binder resin (C-1) is 10-200 mgKOH / g normally, Preferably it is 15-150 mgKOH / g, More preferably, it is 25-100 mgKOH / g.
Within the above range, the solubility in a developer is good and film roughness is not likely to occur, which is preferable.
Moreover, content of (C) binder resin is 0.1 to 80 weight% normally in a total solid, Preferably it is 1 to 60 weight%.

Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.
[(E) Polymerizable monomer]
The colored resin composition of the present invention preferably contains (E) a polymerizable monomer. (E) The polymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).

The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of the photopolymerization initiation system described later when the colored resin composition of the present invention is irradiated with actinic rays. It is. In addition, the (E) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.
(E) Examples of the ethylenic compound in the polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion Is mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  The ethylenic compound may be a monomer having an acid group. The monomer having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (E) polymeric monomer 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.

When it is within the above range, the development and dissolution characteristics are hardly lowered, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.
In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

In the colored resin composition of the present invention, the content of these (E) polymerizable monomers is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content. Further, it is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
The ratio of (E) polymerizable monomer to the total pigment is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more. % By weight or less, preferably 150% by weight or less, more preferably 110% by weight or less.
Within the above range, photocuring is appropriate, poor adhesion during development is difficult to place, the cross-section after development is difficult to reverse taper, and further, peeling phenomenon and omission failure due to lower solubility are difficult to place. preferable.

[(F) Photopolymerization initiation system and / or thermal polymerization initiation system]
The colored resin composition of the present invention preferably contains (F) a photopolymerization initiation system and / or a thermal polymerization initiation system 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 includes a resin having an ethylenic double bond as the component (C), or includes an ethylenic compound as the component (E), it directly absorbs light, or It is preferable to contain a photopolymerization initiating system having a function of generating a polymerization active radical and / or a thermal polymerization initiating system for generating a polymerization active radical by heat. In the present invention, the component (F) as the photopolymerization initiation system is a photopolymerization initiator (hereinafter arbitrarily referred to as (F1) component) to a polymerization accelerator (hereinafter arbitrarily referred to as (F2) component). , Means a mixture in which an additive such as a sensitizing dye (hereinafter, arbitrarily referred to as component (F3)) is used in combination.

(Photopolymerization initiation system)
The colored resin composition of the present invention preferably contains (F) a photopolymerization initiation system. The photopolymerization initiation system is usually used as a mixture of (F1) a photopolymerization initiator, and (F2) a polymerization accelerator added as necessary, (F3) an additive such as a sensitizing dye, and the like. It is a component having a function of generating a polymerization active radical by directly absorbing or photosensitizing to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the photopolymerization initiator constituting the photopolymerization initiation system (F1) include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, etc .; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

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

The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), and the like.
In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.
Examples of the (F2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

These (F1) photopolymerization initiators and (F2) polymerization accelerators may be used alone or in combination of two or more.
Further, (F3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; 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-A-52-112681 JP, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

(F3) 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 of the (F) photopolymerization initiation system is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight based on the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less. If this content is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to development failure.

(Thermal polymerization initiation system)
Specific examples of the thermal polymerization initiation system (thermal polymerization initiator) 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. More specifically, for example, a thermal polymerization initiator described in International Publication No. 2009/107734 pamphlet or the like can be used.
These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.

[Preparation Method of Colored Resin Composition]
The colored resin composition of the present invention comprises a pigment dispersion prepared by the method described in [Preparation Method of Pigment Dispersion], (C) a binder resin, and, if necessary, (E) a polymerizable monomer, And (F) a method of preparing by adding and mixing other components such as a photopolymerization initiation system and / or a thermal polymerization initiation system.
In addition, (C) As mixing of binder resin and other components, you may mix all the components simultaneously or sequentially.

[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 colored resin composition is supplied onto the substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a color filter, and a liquid crystal display device (panel) and an organic EL display device using them will be described.

<Color filter>
The color filter of the present invention has a pixel formed from the colored resin composition of the present invention.
The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.
First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

The substrate used for forming the pixel is not particularly limited as long as it is transparent and has an appropriate strength. For example, a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, or a thermoplastic resin is used. A sheet, an epoxy resin, a thermosetting resin, various glass, etc. are mentioned.
In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.

When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.
The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm as the film thickness after drying.

Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
For example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used as the radiation used when forming the pixels, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

A light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. 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, Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.

Exposure of radiation, 10~10,000J / ^{m 2} is preferred.
Examples of the alkaline developer 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, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

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, further 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.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is, and is used as a part of a color display, a liquid crystal display device, or the like. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Also, a column structure (photo spacer) made of photolithography may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble according to a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<Organic EL display device>
When producing an organic EL display device including the color filter of the present invention, for example, as shown in FIG. 1, on a blue color filter in which pixels 20 are formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is manufactured by laminating the organic light-emitting body 500 through the organic protective layer 30 and the inorganic oxide film 40.

  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. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

<Example>
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 Resin <Synthesis Example 1: Synthesis of Resin A>
114.0 parts by weight of propylene glycol monomethyl ether acetate was placed in a 500 ml four-necked flask and heated to 85 ° C. while nitrogen bubbling was performed. 96.8 parts by weight of benzyl methacrylate, 33.3 parts by weight of methacrylic acid, and 4.925 parts by weight of 2,2′-azobis (isobutyronitrile) were dissolved in 96.45 parts by weight of propylene glycol monomethyl ether acetate. It was dripped over 4 hours. After dropping, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter nitrogen bubbling was stopped, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. Propylene glycol monomethyl ether acetate was added to the obtained resin solution to adjust the solid content concentration to 25% by weight. The weight average molecular weight measured by GPC of the resin A thus obtained was 17000, and the acid value in terms of solid content was 175 mgKOH / g.

<Synthesis Example 2: Synthesis of Resin B>
114.0 parts by weight of propylene glycol monomethyl ether acetate was placed in a 500 ml four-necked flask and heated to 85 ° C. while nitrogen bubbling was performed. In this, 114.4 parts by weight of benzyl methacrylate, 25.9 parts by weight of methacrylic acid and 4.9263 parts by weight of 2,2′-azobis (isobutyronitrile) were dissolved in 96.45 parts by weight of propylene glycol monomethyl ether acetate. It was dripped over 4 hours. After dropping, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter nitrogen bubbling was stopped, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. To this was added 0.6628 parts by weight of tetraethylammonium chloride, and the mixture was stirred and dissolved at 80 ° C. Then, 15.93 parts by weight of 3,4-epoxycyclohexyl-1-methyl acrylate and 23.90 parts by weight of propylene glycol monomethyl ether acetate were added. The mixed solution was added dropwise over 1 hour. The reaction solution was stirred for 30 hours while maintaining the temperature at 80 ° C., after which nitrogen bubbling was stopped, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. Propylene glycol monomethyl ether acetate was added to the resulting resin solution to adjust the solid content concentration to 34% by weight. The weight average molecular weight measured by GPC of the resin B thus obtained was 20000, and the acid value in terms of solid content was 90 mgKOH / g.

<Synthesis Example 3: Synthesis of Resin C>
The mixture was stirred while purging 145.0 parts by weight of propylene glycol monomethyl ether acetate 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 weight average molecular weight Mw measured by GPC of the resin C thus obtained was about 8400, and the acid value in terms of solid content was 80 mgKOH / g.

[2] Preparation of Yellow Pigment Dispersion [2-1] Preparation of Yellow Pigment Dispersion (1) 45.92 parts by weight of propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as “PGMEA”), propylene glycol monomethyl ether (Hereinafter sometimes referred to as “PGME”) 16.00 parts by weight, 12.4 parts by weight of E4GN-GT (manufactured by LANXESS) which is a nickel azo complex represented by the formula (II) as a yellow pigment, a dispersant As a specific polymer in the present invention, DB2000 represented by the following formula (VIII) (solid content concentration: 40% by weight, amine value: 2.0 to 6.0 mgKOH / g, a monomer having a quaternary ammonium group) Content: 34.5 mol%) (made by Big Chemie) 7.89 parts by weight and resin A (solid content concentration 25%) 16.84 parts by weight 2.37 parts by weight of tilcellosolve and 0.71 part by weight of ultrapure water as water were mixed and stirred with a stirrer for 3 hours to prepare a mill base having a solid content concentration of 20% by weight.
The mill base was subjected to dispersion treatment using 600 parts by weight of 0.5 mmφ zirconia beads in a bead mill apparatus at a peripheral speed of 10 m / s and a residence time of 4 hours to obtain a yellow pigment dispersion (1).

[2-2] Preparation of yellow pigment dispersion (2)
[2-1] In the preparation of the yellow pigment dispersion (1), the content of PGMEA was changed to 45.67 parts by weight, and the content of water was changed to 0.96 parts by weight. It carried out similarly to preparation of a pigment dispersion liquid (1), and obtained the yellow pigment dispersion liquid (2).
[2-3] Preparation of yellow pigment dispersion (3) [2-1] In preparation of yellow pigment dispersion (1), the content of PGMEA was 45.65 parts by weight and the content of water was 0.98 wt. Except having changed into the part, it carried out similarly to preparation of [2-1] yellow pigment dispersion liquid (1), and obtained yellow pigment dispersion liquid (3).

[2-4] Preparation of yellow pigment dispersion (4) [2-1] In preparation of yellow pigment dispersion (1), the content of PGMEA was 45.43 parts by weight and the content of water was 1.2 wt. Except having changed into the part, it carried out similarly to preparation of [2-1] yellow pigment dispersion liquid (1), and obtained yellow pigment dispersion liquid (4).
[2-5] Preparation of yellow pigment dispersion (5) [2-1] In preparation of yellow pigment dispersion (1), the content of PGMEA was 46.42 parts by weight and the content of water was 0.26 wt. Except having changed into the part, it carried out similarly to preparation of [2-1] yellow pigment dispersion liquid (1), and obtained yellow pigment dispersion liquid (5).

[2-6] Preparation of yellow pigment dispersion (6) [2-1] In preparation of yellow pigment dispersion (1), the content of PGMEA was 46.30 parts by weight, and the content of water was 0.33 wt. Except having changed into the part, it carried out similarly to preparation of [2-1] yellow pigment dispersion liquid (1), and obtained yellow pigment dispersion liquid (6).
[3] Preparation of Red Pigment Dispersion [3-1] Preparation of Red Pigment Dispersion (1) 51.09 parts by weight of propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as “PGMEA”), propylene glycol monomethyl ether (Hereinafter sometimes referred to as “PGME”) 16.00 parts by weight, C.I. I. Pigment Red (PR) 177, 12.63 parts by weight, DB2000 (solid content 40%) as a dispersant (7.89 parts by weight, manufactured by Big Big Chemie) and Resin B (solid content 34%) 12 .38 parts by weight were mixed and stirred with a stirrer for 3 hours to prepare a mill base having a solid concentration of 20% by weight.

The mill base was subjected to a dispersion treatment using 600 parts by weight of 0.5 mmφ zirconia beads in a bead mill apparatus at a peripheral speed of 10 m / s and a residence time of 4 hours to obtain a red pigment dispersion (1).
[3-2] Preparation of red pigment dispersion (2) PGMEA 55.65 parts by weight, pigment C.I. I. 7.50 parts by weight of Pigment Red (PR) 254, LPN6919 (manufactured by Big Chemie) (solid content concentration 40%) as a dispersant, 7.50 parts by weight, Resin B synthesized in Synthesis Example 2 (solid content) 7.35 parts by weight of (concentration 34%) was mixed and stirred with a stirrer for 3 hours to prepare a mill base having a solid content concentration of 20% by weight. The mill base was subjected to a dispersion treatment using 600 parts by weight of 0.5 mmφ zirconia beads in a bead mill apparatus at a peripheral speed of 10 m / s and a residence time of 3 hours to obtain a red pigment dispersion (2).

[4] Measurement of water content of pigment dispersion The yellow pigment dispersions (1) to (6) prepared in the above [2] Preparation of yellow pigment dispersion are described in <Measurement method of water content> below. The water content was measured by this method.
The results are summarized in Table 1.

<Method for measuring moisture content>
In the present invention, the water content of the pigment dispersion was measured by the Karl Fischer volumetric titration method under the following conditions.
・ Device: Karl Fischer moisture meter KF-100 (Mitsubishi Chemical Analytech)
・ Injection volume: 1 mL
-Titration solvent: Aquamicron titrant SS-Z 3mg
Titer 2.5~3.5mgH ₂ O / ml
・ Dehydrated solvent: Aquamicron dehydrated solvent GEX
Measurement range: 0.1-999 mg H ₂ O
[4] Viscosity and contrast evaluation of yellow pigment dispersion The yellow pigment dispersion prepared in [2-1] to [2-6] was prepared, and the viscosity immediately after the preparation and the viscosity after 24 hours were measured.

The viscosity was measured at room temperature (23 ° C.) and 20 rpm using an E-type viscometer “RE-80L” (manufactured by Toki Sangyo Co., Ltd.).
The results are summarized in Table 3.
Next, a colored resin composition was prepared with the composition shown in Table 2, and the contrast was measured.
Specifically, using the yellow pigment dispersion prepared in [2-1] to [2-6], binder resin C, dipentaerythritol hexaacrylate, IRGACURE OXE02 (BASF), 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure907 BASF) and surfactant F-475 (manufactured by DIC) were mixed at a weight ratio shown in Table 2, and the solid content was determined with the solvent PGMEA. The concentration was adjusted to 20% to obtain a yellow colored resin composition.

Each yellow colored resin composition was spin-coated on a glass substrate AN100 (manufactured by Asahi Glass Co., Ltd.) and prebaked for 3 minutes on an 80 ° C. hot plate. The coating rotation speed was adjusted so that the film thickness would be the color coordinate y = 0.437 after post-baking.
Next, after exposure at 60 mJ / cm ² with a high-pressure mercury lamp, 0.04 wt% potassium hydroxide aqueous solution was used, and spray development was performed at a developer temperature of 23 ° C. and 0.25 MPa pressure for 40 seconds.
After development, the substrate was rinsed with sufficient water and then dried with clean air. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes.

Next, the substrate is placed between two polarizing plates in close contact with no gap, and a light intensity A (cd / cd) when the polarizing plates are orthogonal using a color luminance meter ("BM-5AS" manufactured by Topcon). from the ratio of cm ²⁾ and the light amount at the time of parallel B (cd / cm ^2), and calculates the contrast by the following equation (1). These results are summarized in Table 3.
C = B / A (1)

In Table 3 above, the contrast is the value of the contrast ratio when the contrast of the substrate prepared using the yellow colored resin composition prepared using the yellow pigment dispersion (2) of Example 2 is taken as 100. .
As shown in Table 3, the pigment dispersion of the present invention has a low viscosity after 24 hours from the dispersion.
That is, since the colored resin composition containing the pigment dispersion of the present invention is difficult to increase the viscosity, that is, it is possible to suppress a decrease in yield in the color filter manufacturing process due to the increase in the viscosity of the composition.

Furthermore, the color filters formed using the colored resin composition of the present invention all have a practical level of contrast.
[5] Evaluation of Red Pigment Colored Resin Composition [5-1] Preparation of Red Pigment Colored Resin Composition Red pigment coloring shown in Table 4 using yellow pigment dispersions (1), (3) and (6) A resin composition was prepared.

[5-2] Resolubility of Red Pigment Colored Resin Composition Using the compositions of Examples 5 and 6 and Comparative Example 3, resolubility was evaluated.
The results of measuring the re-solubility are shown in Table 5.
(Resolubility evaluation method)
When evaluating the colored curable composition according to the following applicability evaluation method, a control is automatically performed for attaching a test piece to the arm of the actuator and repeatedly taking the tip into and out of the colored curable composition filled in the bottle. The device was used.

<Applicability evaluation method>
(I) At an atmospheric temperature of 23 ° C., a tip portion of 20 mm in the vertical direction of a glass test piece of length 100 mm × width 5 mm × thickness 0.7 mm was immersed in the curable composition at a rate of 12.5 mm / second,
Then hold for 4 seconds.
(Ii) The glass test piece is taken out of the curable composition at a speed of 12.5 mm / second and held vertically with the tip of the glass test piece down, and then the ambient temperature is 23 ° C., the humidity is 55%, and the wind speed. Dry for 56 seconds under conditions of 0.5 ± 0.2 m / sec.

(Iii) Steps (i) and (ii) are repeated a total of 120 times to form a deposit (a) derived from the curable composition on the glass test piece.
Table 5 shows the result of the formation area (area of undissolved material) of deposits on the entire surface of the substrate.

As shown in Table 5, the colored resin composition of the present invention has little undissolved residue, that is, high resolubility.
That is, even when used in the ink jet method or the die coating method, it is difficult to affect the agglomeration drying, and it is possible to suppress a decrease in yield in color filter production due to the agglomerates.

DESCRIPTION OF SYMBOLS 100 Organic EL element 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 500 Organic light-emitting body 51 Hole injection layer 54 Electron injection layer

Claims (11)

In a pigment dispersion containing (A) a yellow pigment, (B) a solvent and (D) a dispersant,
As the (D) dispersant, a polymer is contained,
The polymer has a primary to tertiary amino group and / or a quaternary ammonium group in the side chain,
In the monomer composition constituting the polymer, the content ratio of the monomer having the primary to tertiary amino group and / or quaternary ammonium group is 20 mol% or more,
Further, the pigment dispersion is characterized in that the water content in the pigment dispersion is 0.4 wt% or more and 1.8 wt% or less. The (A) yellow pigment contains a compound obtained by inserting another compound into a 1: 1 complex of azobarbituric acid represented by the following formula (II) with nickel or a compatible isomer thereof. The pigment dispersion according to claim 1, characterized in that it is characterized in that

  The pigment dispersion according to claim 1 or 2, wherein the (D) dispersant is a (meth) acrylic block copolymer. The pigment dispersion according to any one of claims 1 to 3, wherein the content of the dispersant (D) with respect to the (A) yellow pigment is 40% by weight or less. The pigment dispersion according to any one of claims 1 to 4, wherein an alcohol solvent is contained in the solvent (B) in an amount of 10 wt% to 40 wt%.   A colored resin composition comprising the pigment dispersion according to any one of claims 1 to 5 and (C) a binder resin.   The colored resin composition according to claim 6, further comprising (E) a polymerizable monomer.   The colored resin composition according to claim 6 or 7, further comprising (F) a photopolymerization initiation system and / or a thermal polymerization initiation system.   It has a pixel formed using the colored resin composition as described in any one of Claims 6-8, The color filter characterized by the above-mentioned.   A liquid crystal display device comprising the color filter according to claim 9.   An organic EL display device comprising the color filter according to claim 9.

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