WO2015008734A1

WO2015008734A1 - Coloring composition for color filter

Info

Publication number: WO2015008734A1
Application number: PCT/JP2014/068742
Authority: WO
Inventors: 剛江川
Original assignee: 花王株式会社
Priority date: 2013-07-15
Filing date: 2014-07-14
Publication date: 2015-01-22
Also published as: JPWO2015008734A1; CN105378513A; TW201512314A; KR20160032102A

Abstract

　The present invention provides: a coloring composition for a color filter that has an excellent brightness and contrast ratio and enables a satisfactory heat resistance to be obtained; a color filter; a method for manufacturing same; and a pigment composition. [1] A coloring composition for a color filter containing a pigment, a dispersant, and a solvent, the pigment containing a compound (a) represented by general formula (Ia) and a compound (b) represented by general formula (Ib), the amount of compound (b) being contained in relation to the total of compound (a) and compound (b) being 3 to 90 mol%; [2] a color filter obtained using the coloring composition; [3] a method for manufacturing same; and [4] a pigment composition containing a compound (a) represented by general formula (Ia) and a compound (b) represented by general formula (Ib), the amount of compound (b) being contained in relation to the total of compound (a) and compound (b) being 3 to 90 mol%.

Description

Coloring composition for color filter

The present invention relates to a color filter coloring composition, a color filter, a method for producing the same, and a pigment composition.

A color filter used in a liquid crystal display device is a photolithography in which a colored composition in which a pigment dispersion is blended with a resin or the like is applied to a transparent substrate such as glass to form a coating film, which is exposed, cured, developed, and thermally cured. Manufactured by law. The pigment dispersion used here is a pigment dispersion in which a pigment is dispersed in a solvent. As a method for producing a pigment dispersion, a production method using a polymer dispersant such as a graft polymer is known, and various methods are available. In order to satisfy the required performance, improvement of the dispersant has been studied.

For example, Patent Document 1 discloses a composition containing a diketopyrrolopyrrole colorant having 0.2 or more bromo groups for the purpose of high brightness, high contrast, and suppression of contrast reduction during heating.
Patent Document 2 discloses a diketopyrrolopyrrole pigment having two bromo groups, a bromo group, and other substituents for the purpose of suppressing the crystal precipitation of the diketopyrrolopyrrole pigment during heating with high brightness and high contrast. A diketopyrrolopyrrole pigment composition characterized in that the mass ratio of the diketopyrrolopyrrole pigment is 97: 3 to 85:15 is disclosed.
Patent Document 3 discloses a coloring composition comprising a diketopyrrolopyrrole pigment having two bromo groups and an alkali-soluble photosensitive resin for the purpose of suppressing crystal precipitation of the diketopyrrolopyrrole pigment during heating with high brightness and high contrast. Things are disclosed.

Special table 2011-523433 gazette JP 2012-155232 A JP 2012-21970 A

The present invention relates to [1] to [4].
[1] A compound containing a pigment, a dispersant, and a solvent, wherein the pigment is represented by the general formula (Ia) (hereinafter also referred to as “compound (a)”), and a compound represented by the general formula (Ib) (Hereinafter also referred to as “compound (b)”), and the content of the compound (b) relative to the sum of the compound (a) and the compound (b) is 3 mol% or more and 90 mol% or less. Composition.

[2] Color filter obtained using the colored composition of [1] [3] A method for producing a color filter, comprising the following steps (a) and (b).
Step (a): A step of applying the colored composition described in [1] onto a substrate, photocuring and developing to obtain a coating film. Step (b): The coating film obtained in the step (a) is 200 to The process of obtaining a cured film by heating to 300 ° C. [4] The compound (a) and the compound (b) are contained, and the content of the compound (b) with respect to the total of the compound (a) and the compound (b) is 3 mol%. A pigment composition that is 90 mol% or more.

Detailed Description of the Invention

In the production of a color filter using a photolithography method, the coloring composition used is a pigment, particularly a diketopyrrolopyrrole, which causes a decrease in brightness and contrast ratio during the post-baking process after pattern formation. It is necessary to suppress the generation of crystalline foreign substances that are thought to be derived from pigment sublimation and recrystallization.
On the other hand, color filters are required to have high brightness and contrast ratio as the display image becomes brighter and finer. As a method for improving the brightness and contrast ratio, the pigment is made finer. However, since the specific surface area of the pigment is increased, the generation of crystalline foreign substances considered to be derived from the sublimation and recrystallization of the pigment occurs. Since it tends to occur, it is difficult to achieve both high luminance and contrast ratio and to suppress the generation of crystalline foreign matter. Accordingly, there is a demand for a coloring composition for a color filter having high luminance, a contrast ratio, and a so-called good heat resistance that suppresses generation of crystalline foreign matters.
An object of the present invention is to provide a coloring composition for a color filter, a color filter, a method for producing the same, and a pigment composition, which are excellent in luminance and contrast ratio and obtain good heat resistance.

In the coloring composition for color filters, the present inventors include a pigment containing the compound (a) represented by the general formula (Ia) and the compound (b) represented by the general formula (Ib) at a specific ratio. It has been found that a color filter having excellent luminance and contrast ratio and having good heat resistance can be obtained.

According to the present invention, it is possible to provide a novel color filter color composition, color filter, method for producing the same, and pigment composition which are excellent in luminance and contrast ratio and obtain good heat resistance.

The coloring composition for a color filter of the present invention contains a pigment, a dispersant, and a solvent, the pigment contains the compound (a) and the compound (b), and the compound with respect to the sum of the compound (a) and the compound (b). The content of (b) is 3 mol% or more and 90 mol% or less. By using a combination of compound (a) and compound (b) as pigments, a synergistic effect is exhibited, and these contrast ratios and luminance are excellent, and furthermore, a color composition for color filters with high heat resistance is obtained. It is done.

When the compound (a) is used alone, the contrast ratio is excellent, but crystalline foreign matters are likely to be generated during the post-baking step after pattern formation, and the heat resistance is poor. The foreign matter is considered to be derived from sublimation and recrystallization of the compound (a).
On the other hand, when a specific amount of the compound (b) is allowed to coexist with the compound (a), the heat resistance is excellent and the luminance is further improved. The reason for this is not clear, but is estimated as follows. First, the compound (b) that is different only in substituents can easily interact with the compound (a). Therefore, sublimation during post-baking can be suppressed and recrystallization can be prevented, so that the heat resistance is greatly improved. Moreover, since it contributes also to suppression of the re-aggregation of the pigment at the time of coating-film preparation by the said interaction, the brightness | luminance of a color filter improves, maintaining an excellent contrast ratio. Furthermore, since both the compound (a) and the compound (b) have a highly symmetric chemical structure, they interact more easily and the electron transition energy is kept sharp, so that the above-described effects can be obtained. More prominently expressed.
However, the above is estimation and the effect of the present invention is not limited to the above mechanism.
Hereafter, each component, process, etc. used for this invention are demonstrated.

[Pigment]
The pigment of the present invention contains a compound (a) represented by the general formula (Ia) and a compound (b) represented by the general formula (Ib).

In the compound (a), the substitution position on the phenyl group of the bromine atom may be independently any of the ortho position, the meta position, and the para position. Independently, it is ortho-position or para-position, more preferably para-position.
In the compound (b), the substitution position on the phenyl group of the chlorine atom may be independently any of the ortho position, the meta position, and the para position. Independently, it is ortho-position or para-position, more preferably para-position.
Compound (a) and compound (b) can be produced, for example, by referring to WO2009 / 144115.
As a suitable example of a commercial item of a compound (b), BASF Japan Ltd. make, C.I. I. Pigment Red 254 (hereinafter also referred to as “PR254”) “Irgaphor Red B-CF”, “Irgaphor Red BK-CF”, “Irgaphor Red BT-CF”, “Irgazin DPP Red BO”, “Irgazin DPP Red BL”, “Cromophtal DPP Red BP”, “Cromophtal DPP Red BOC”; PR254 “HOSTAPERM RED D2B-COF01”, “HOSTAPERM RED D2B-COFLV3781” manufactured by Clariant Co., Ltd., and the like.

The content of the compound (b) with respect to the total of the compound (a) and the compound (b) is 3 mol% or more and 90 mol% or less from the viewpoint of luminance, contrast ratio, and heat resistance.
The content of the compound (b) with respect to the total of the compound (a) and the compound (b) is preferably 6 mol% or more, more preferably 12 mol% or more, still more preferably 15 mol% or more, from the viewpoint of luminance and heat resistance. More preferably, it is 17 mol% or more, and from the viewpoint of luminance and contrast ratio, it is preferably 83 mol% or less, more preferably 78 mol% or less, still more preferably 58 mol% or less, still more preferably 40 mol% or less, still more preferably 35 mol. % Or less, more preferably 30 mol% or less, more preferably 25 mol% or less, and still more preferably 20 mol% or less. Moreover, from a heat resistant viewpoint, More preferably, it is 26 mol% or more, More preferably, it is 45 mol% or more.

The pigment of this invention may contain pigments other than the said compound (a) and compound (b) in the range which does not impair the effect of this invention. Further, the pigment of the present invention contains diketopyrrolopyrrole pigments other than the compounds (a) and (b) (hereinafter also referred to as “other diketopyrrolopyrrole pigments” or “other DPP pigments”). It may be. In the present specification, the compound (a), the compound (b), and other diketopyrrolopyrrole pigments are collectively referred to simply as “diketopyrrolopyrrole pigment” or “DPP pigment”.
Other DPP pigments include C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 270, C.I. I. Pigment red 272, C.I. I. Pigment orange 71, C.I. I. Pigment Orange 73 and the like. Among these, compounds represented by the following general formula (Id) other than the compound (a) and the compound (b) are preferable.

In Formula (Id), X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, or an aromatic hydrocarbon group that may be substituted with a hydrogen atom, and Y ¹ and Y ² are each Independently, it represents a hydrogen atom, —SO ₃ H, —SO ₃ ⁻ M ⁺ , and M ⁺ represents a cation. The halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom.

Examples of pigments other than the DPP pigment include azo pigments, condensed polycyclic pigments, lake pigments, and the like.
As the azo pigment, C.I. I. Insoluble azo pigments such as CI Pigment Red 3; I. Soluble red azo pigments such as CI Pigment Red 48: 1; I. And condensed azo pigments such as CI Pigment Red 144.
Examples of the condensed polycyclic pigment include C.I. I. Anthraquinone pigments such as CI Pigment Red 177; I. Perylene pigments such as CI Pigment Red 123; I. Perinone pigments such as C.I. Pigment Orange 43; I. Quinacridone pigments such as C.I. Pigment Red 122; I. Dioxazine pigments such as CI Pigment Violet 23, C.I. I. Pigment Yellow 109 and other isoindolinone pigments, C.I. I. Pigment orange 66, C.I. I. Pigment Yellow 139 and the like, isoindoline pigments such as C.I. I. Quinophthalone pigments such as CI Pigment Yellow 138; I. Pigment azo complex pigments such as CI Pigment Yellow 150, C.I. I. And indigo pigments such as CI Pigment Red 88.
Among these, from the viewpoint of adjusting chromaticity, preferably an anthraquinone pigment, more preferably C.I. I. Pigment Red 177 (hereinafter also referred to as “PR177”).

The total content of the compound (a) and the compound (b) in the pigment of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably from the viewpoint of expressing the effect of the present invention. Is 50% by mass or more, and more preferably 60% by mass or more. From the viewpoint of optimizing the color characteristics, it is preferably 100% by mass or less, more preferably 90% by mass or less.

The content of the DPP pigment in the pigment of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and still more preferably from the viewpoint of expressing the effects of the present invention. From the viewpoint of optimizing the color characteristics, it is preferably 100% by mass or less, and more preferably 90% by mass or less.
The total content of the compound (a) and the compound (b) in the DPP pigment of the present invention is preferably 80% by mass or more, more preferably 85% by mass or more, further from the viewpoint of expressing the effect of the present invention. The content is preferably 90% by mass or more, and preferably 100% by mass or less, more preferably 95% by mass or less from the viewpoint of optimizing color characteristics.
The content of the pigment other than the DPP pigment is, for example, 0% by mass or more, preferably 10% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass or less, More preferably, it is 40 mass% or less.

[Dispersant]
The dispersant preferably has a cationic group from the viewpoint of improving the dispersibility of the pigment and improving the contrast ratio of the coloring composition. It is considered that the cationic group of the dispersant is efficiently adsorbed on the surface of the pigment particles, and the dispersibility and the contrast ratio are excellent. Examples of the cationic group include at least one selected from a quaternary ammonium group and an ammonium group (—NH ₃ ⁺ ), preferably a quaternary ammonium group.
The dispersant is preferably a polymer dispersant.
The dispersant preferably has a cationic group in the main chain.
The dispersant preferably has a polyalkylene oxide chain and more preferably has a polyalkylene oxide chain as a side chain from the viewpoint of improving the dispersibility of the pigment and improving the contrast ratio of the coloring composition. It is considered that when the polyalkylene oxide chain imparts a steric repulsive force between the pigment particles, the dispersibility is improved and the contrast ratio is also improved.
From the viewpoint of dispersibility and storage stability, the weight average molecular weight of the dispersant is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, and even more preferably 3,500 or more. In addition, it is preferably 35,000 or less, more preferably 20,000 or less, and still more preferably 10,000 or less. The weight average molecular weight can be measured by gel permeation chromatography, and the specific measurement method is the method described in the examples.
The dispersant is preferably a dispersant represented by the general formula (II) (hereinafter also referred to as “dispersant (1)”), a structural unit derived from dialkylaminoalkyl (meth) acrylamide, and an alkoxypolyalkylene glycol. And a polymer dispersant (hereinafter also referred to as “dispersant (2)”) having a structural unit derived from (meth) acrylate and having a quaternization rate of 10 to 80 mol%. Among these, from the viewpoint of brightness and contrast ratio, the dispersant (1) is more preferable.

<Dispersant (1)>
The dispersant (1) is a compound represented by the following general formula (II).

Wherein, R ^1, R ^2, R ³ and R ⁴ are the same or different and have good hydrocarbon group partially carbon atoms which may be substituted by a hydroxyl group 1 to 10 of the hydrogen atoms , R ⁵ represents an alkanediyl group having 1 to 18 carbon atoms (where R ⁵ adjacent to R ¹ represents a single bond), and R ⁶ represents an alkanediyl group having 1 to 4 carbon atoms. , R ⁷ represents an alkanediyl group having 2 to 4 carbon atoms, R ⁸ represents a hydrocarbon group having 1 to 18 carbon atoms, a represents an average addition mole number, and 1 to 100, M ¹ ) ⁻ and (M ² ) ⁻ each independently represents an anion, n, m and k represent the average number of structural units, (n + m + k) is 1 or more and 22 or less, and n is 1 or more and 22 or less. , M is 0 or more and 21 or less, and k is 0 or more and 21 or less. Note that when there are a plurality of R ⁷ Os, they may be the same or different, and each structural unit whose average number of structural units is represented by n, m, k may be in any arrangement order.

(N + m + k) is 22 or less from the viewpoint of the contrast ratio, preferably 11 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, and 1 Or more, preferably 2 or more. Further, it is even more preferably 2 from the viewpoint of an excellent contrast ratio.
From the viewpoint of contrast ratio, n is 22 or less, preferably 11 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, and 1 or more. Yes, preferably 2 or more. Further, it is even more preferably 2 from the viewpoint of an excellent contrast ratio.
From the viewpoint of contrast ratio, m and k are each independently 21 or less, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, still more preferably 1 or less, and 0 or more. is there. Further, from the viewpoint of an excellent contrast ratio, it is preferably 0.
The ratio of n to (n + m + k) (n / (n + m + k)) is preferably 0.3 or more, more preferably 0.6 or more, still more preferably 0.8 or more, and still more preferably from the viewpoint of the contrast ratio. 0.9 or more, preferably 1.0 or less, and even more preferably 1.0.
The structural units whose average number of structural units is indicated by n, m, and k may be in any arrangement order. When one or more of n, m, and k are plural, each structural unit may be in any arrangement order such as random or block.

The number of carbon atoms of R ¹ , R ² , and R ⁴ is 10 or less, preferably 8 or less, more preferably 6 or less, and even more preferably 1 from the viewpoint of contrast ratio.
Examples of R ¹ , R ² , and R ⁴ include at least one selected from a methyl group, an ethyl group, a butyl group, a hexyl group, a hydroxymethyl group, a hydroxybutyl group, and a hydroxyhexyl group. R ¹ , R ² , and R ⁴ are preferably a hydrocarbon group not substituted with a hydroxyl group, more preferably at least one selected from a methyl group and an ethyl group, and even more preferably a methyl group. .
The carbon number of the hydrocarbon group of R ¹ and R ² is preferably 5 or less, more preferably 3 or less, still more preferably 2 or less, and even more preferably 1 from the viewpoint of contrast ratio.
The number of carbon atoms of the hydrocarbon group of R ⁴ is preferably 4 or less, more preferably 3 or less, from the viewpoint of ease of production of the dispersant (1). R ⁴ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

From the viewpoint of contrast ratio, the carbon number of the alkanediyl group of R ⁵ is preferably 2 or more, more preferably 3 or more, and 18 or less, preferably 14 or less, more preferably 12 or less, even more Preferably it is 10 or less, and more preferably 6 or less.
Examples of the alkanediyl group of R ⁵ include at least one selected from an ethylene group, various propanediyl groups, various hexanediyl groups, and various nonanediyl groups. From the viewpoint of contrast ratio, propane 1,3- At least one selected from a diyl group and a hexane 1,6-diyl group, more preferably a propane 1,3-diyl group.

The number of carbon atoms of R ^6, from the viewpoint of easy production of the dispersant (1), no greater than 4, preferably 3 or less, more preferably 2 or less, more preferably 1. R ⁶ is preferably a methylene group.

From the viewpoint of contrast ratio, the carbon number of R ⁷ is 4 or less, preferably 3 or less, or 2 or more. R ⁷ is preferably at least one selected from an ethylene group and a propylene group.

From the viewpoint of contrast ratio, a is 1 or more, preferably 15 or more, more preferably 21 or more, more preferably 30 or more, still more preferably 40 or more, and 100 or less, preferably 95 or less. More preferably, it is 70 or less, More preferably, it is 50 or less.

When a plurality of (R ⁷ O) are present, they may be the same or different, and the sequence of (R ⁷ O) may be either random or block.
In addition, (R ⁷ O) preferably includes a structural unit derived from propylene oxide, and more preferably includes a structural unit derived from propylene oxide and a structural unit derived from ethylene oxide, from the viewpoint of affinity with the solvent.

In the general formula (II), (R ⁷ O) _a is preferably a structural unit represented by the following general formula (II-a) from the viewpoint of contrast ratio.

In the formula (II-a), PO represents a propylene oxide unit, EO represents an ethylene oxide unit, b and c represent average addition mole numbers, b is 0 to 100, c is 0 to 100, b + c is 1 to 100. * Represents a binding site. In the formula (II-a), the structural unit is preferably a block polymer. The (PO) terminal side of the formula (II-a) is bonded to R ⁸ O, and the (EO) terminal side. Is preferably bonded to a carbonyl group.
b is preferably 10 or more, more preferably 21 or more, and further preferably 25 or more, from the viewpoint of the contrast ratio, and preferably 60 or less, more preferably from the viewpoint of ease of production of the dispersant (1). Is 50 or less, more preferably 35 or less.
From the viewpoint of contrast ratio, c is preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, and is preferably 95 or less, more preferably 70 or less, still more preferably 50 or less, and even more preferably. Is 30 or less, more preferably 20 or less.
The total of b and c (b + c) is preferably 15 or more, more preferably 21 or more, still more preferably 30 or more, still more preferably 40 or more, and preferably 95 or less, from the viewpoint of the contrast ratio. Preferably it is 70 or less, More preferably, it is 50 or less.
The ratio of b to the total of b and c (b / (b + c)) is preferably 0.2 or more, more preferably 0.4 or more, still more preferably 0.5 or more, from the viewpoint of the contrast ratio. From the viewpoint of ease of production of the dispersant (1), it is preferably 0.97 or less, more preferably 0.86 or less, and still more preferably 0.8 or less.

The carbon number of R ⁸ is 1 or more from the viewpoint of dispersibility and ease of production of the coating film, preferably 6 or more, more preferably 10 or more, and 18 or less, preferably 16 or less, More preferably, it is 14 or less, More preferably, it is 12 or less.
Examples of R ⁸ include at least one selected from a methyl group, a decyl group, a lauryl group, an oleyl group, a stearyl group, a p-octylphenyl group, and a p-nonylphenyl group. R ⁸ is preferably an aliphatic hydrocarbon group, more preferably at least one selected from a methyl group, a decyl group, and a lauryl group, and more preferably, from the viewpoint of dispersibility and ease of production of the coating film. Is a lauryl group.

The carbon number of R ³ is 10 or less from the viewpoint of the contrast ratio, preferably 7 or less, more preferably 4 or less, still more preferably 2 or less, and 1 or more. R ³ includes at least one selected from a methyl group, an ethyl group, and a benzyl group, and a methyl group is preferable from the viewpoint of contrast ratio.

(M ¹ ) ⁻ and (M ² ) ⁻ are each independently an anion, preferably from a halide ion, an alkyl sulfate ion, an alkylbenzene sulfonate ion, and an alkyl carbonate ion, from the viewpoint of contrast ratio and ease of production. It is one kind selected.

(M ¹ ) ⁻ is preferably a halide ion, more preferably a chloride ion, from the viewpoint of the contrast ratio and ease of production of the dispersant (1).

(M ² ) ⁻ is preferably at least selected from CH ₃ SO ₄ ⁻ , C ₂ H ₅ SO ₄ ^— and CH ₃ C ₆ H ₄ SO ₃ ^— from the viewpoint of ease of production of the dispersant (1). One, more preferably at least one selected from CH ₃ SO ₄ ^— and C ₂ H ₅ SO ₄ ^— , and more preferably CH ₃ SO ₄ ^— . (M ² ) ⁻ is preferably a halide ion, more preferably a chloride ion, from the viewpoint of the contrast ratio.

From the above, from the viewpoint of the contrast ratio, m and k are preferably 0. More specifically, the dispersant (1) is preferably a compound represented by the following general formula (II-1).

[Wherein R ¹ , R ² and R ⁴ may be the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms in which a part of hydrogen atoms may be substituted with a hydroxyl group; R ⁵ represents an alkanediyl group having 1 to 18 carbon atoms, R ⁶ represents an alkanediyl group having 1 to 4 carbon atoms, R ⁷ represents an alkanediyl group having 2 to 4 carbon atoms, R ⁸ Represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a represents an average addition mole number, 1 to 100, (M ¹ ) ⁻ represents an anion, and n represents an average number of structural units. 1 or more and 5 or less. When a plurality of R ⁷ Os are present, they may be the same or different. ]

In the formula (II-1), preferable R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , a, (M ¹ ) ⁻ , and n are the same as those in the above formula (II). It is.

The weight average molecular weight of the dispersant (1) is preferably 2,000 or more, more preferably 3,000 or more, still more preferably 3,500 or more, and preferably 35,000 or less from the viewpoint of the contrast ratio. More preferably, it is 20,000 or less, More preferably, it is 10,000 or less. The measuring method of a weight average molecular weight is based on the method as described in an Example.

<Method for producing dispersant (1)>
The dispersant (1) is, for example, a reaction between a halogenated alkyl ester compound represented by the following general formula (III) and an amine compound represented by the following general formula (IV), and further, if necessary, quaternary It is obtained by reacting an agent.

[In the formula (III), R ⁶ , R ⁷ , R ⁸ and a are the same as those described above, and X represents a halogen atom. ]

[In the formula (IV), R ¹ , R ² , R ⁴ , R ⁵ and (n + m + k) are the same as those described above. ]
The dispersant (1) represented by the general formula (II) is obtained by reacting the raw materials in the absence of a solvent or in a solvent.
The solvent used in the reaction is preferably a non-aqueous solvent described later, more preferably an ether solvent. The ether solvent is preferably (poly) alkylene glycol monoalkyl ether acetate, more preferably propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”) and diethylene glycol monobutyl ether acetate (hereinafter also referred to as “BCA”). At least one selected, more preferably PGMEA.

In the halogenated alkyl ester represented by the general formula (III), for example, an alcohol having an R ⁸ hydrocarbon group and an alkylene oxide compound forming R ⁷ O are reacted in the presence of a basic substance. To obtain an alkoxypolyalkylene glycol, followed by dehydration condensation with a carboxylic acid having an alkyl halide. In the present specification, “alkoxy” is a concept representing R ^A O— (R ^A represents a hydrocarbon group containing a saturated or unsaturated aliphatic hydrocarbon group).

In the reaction for obtaining the dispersant (1), it is represented by the general formula (III) with respect to the number of amine functional groups of the amine compound represented by the general formula (IV) ((n + m + k) × molar amount in the general formula (IV)). The ratio of the halogenated alkyl ester compound (molar amount) can be appropriately set according to the target compound, and is, for example, 0.3 to 1.2. By appropriately setting the above ratio, it is possible to obtain a compound in which the n and m numbers with respect to (n + m + k) in the general formula (II) are adjusted. The reaction amount ratio between the amine compound and the halogenated alkyl ester compound is a molar equivalent calculated from the amine value of the amine compound and the halogenated alkyl ester compound from the viewpoint of more accurately controlling the number of n and m. It is preferable to adjust based on the molar equivalent calculated from the amount of halogen.
Moreover, it is preferable that the reaction atmosphere in the said process is inert gas atmosphere, such as nitrogen gas atmosphere and argon.
The reaction temperature in this step is, for example, preferably 50 ° C. or higher, more preferably 80 ° C. or higher, and preferably 100 ° C. or lower.

In the general formula (II), a compound in which k exceeds 0 can be obtained, for example, by treating a compound in which the m in general formula (II) exceeds 0 with a quaternizing agent.
As the quaternizing agent, a substance that reacts with a tertiary amino group to convert the amino group to quaternary ammonium is used. For example, dialkyl sulfate such as dimethyl sulfate or diethyl sulfate; halogenation such as methyl chloride or methyl iodide Alkyl; aryl halides such as benzyl chloride; alkyl p-toluenesulfonates such as methyl p-toluenesulfonate and ethyl p-toluenesulfonate. From the viewpoint of reactivity, dimethyl sulfate is preferable, and from the viewpoint of contrast ratio, methyl chloride is preferable.

(Dispersant (2))
The dispersant (2) includes a structural unit derived from dialkylaminoalkyl (meth) acrylamide (hereinafter also referred to as “(2A)”) and an alkoxypolyalkylene glycol (meth) acrylate (hereinafter also referred to as “(2B)”). And derived structural units.
The quaternization rate of the dispersant (2) is preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more, still more preferably 25 mol% or more, from the viewpoint of the contrast ratio. From the same viewpoint, it is preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less, still more preferably 50 mol% or less, and still more preferably 40 mol% or less.
The “quaternization rate” refers to the ratio (mol%) of the number of molar equivalents of quaternary ammonium groups to the total number of molar equivalents of tertiary amino groups and quaternary ammonium groups contained in the dispersant (2). means. The quaternization rate can be measured by the method described in the examples.
The dispersant (2) having the quaternization rate can be obtained by, for example, quaternizing the structural unit derived from (2A), but a monomer having (2A), (2B) and a quaternary ammonium group. (Hereinafter also referred to as “(2C)”).
When the amine value before quaternization of the dispersant (2) is unknown, or in the case of the dispersant (2) obtained by copolymerization with a monomer having a quaternary ammonium group, nuclear magnetic resonance The value calculated from the content of the tertiary amino group and quaternary ammonium group identified by (NMR) is regarded as the quaternization rate.

The content of the structural unit derived from (2A) in the total of the structural unit derived from (2A) and the structural unit derived from (2B) [(2A) / (2A + 2B) × 100] is preferable from the viewpoint of the contrast ratio. Is 5% by mass or more, more preferably 10% by mass or more, still more preferably 13% by mass or more, still more preferably 15% by mass or more, and preferably 49% by mass or less, more preferably 40% by mass or less, More preferably, it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 22.5 mass% or less. In addition, let the said mass ratio be the conversion mass of the structural unit which excluded the mass of the quaternizing agent origin component, ie, the alkyl group derived from a quaternizing agent, and the anion component of a pair.
The dispersant (2) may contain a structural unit derived from a monomer other than (2A) and (2B), but the content of the structural unit derived from (2A) and (2B) is dispersed. In the agent (2), it is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and still more preferably only from structural units derived from (2A) and (2B). Become.

The weight average molecular weight of the dispersant (2) is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 11,000 or more, and preferably 50,000 or less from the viewpoint of the contrast ratio. More preferably, it is 40,000 or less, More preferably, it is 20,000 or less, More preferably, it is 15,000 or less. The measuring method of a weight average molecular weight is based on the method as described in an Example. In the dispersant (2), the weight average molecular weight before quaternization is regarded as the weight average molecular weight of the dispersant (2).

<Dialkylaminoalkyl (meth) acrylamide (2A)>
The dialkylaminoalkyl (meth) acrylamide (2A) is preferably dimethylaminoalkyl (meth) acrylamide or diethylaminoalkyl (meth) acrylamide, more preferably dimethylaminoalkyl (meth) acrylamide, more preferably from the viewpoint of contrast ratio. It is dimethylaminoalkylacrylamide, and more preferably N, N-dimethylaminopropylacrylamide (hereinafter also referred to as “DMAPAA”) from the viewpoint of strong adsorptivity to the pigment surface. In the present specification, “(meth) acrylamide” means at least one selected from acrylamide and methacrylamide.

The tertiary amino group of the structural unit derived from (2A) is preferably quaternized. In that case, the alkyl group introduced into the tertiary amino group is preferably an ethyl group or a methyl group, more preferably a methyl group, from the viewpoint of the ease of production of the dispersant (2) and the contrast ratio. Further, the counter ion of the quaternary ammonium group is preferably at least one selected from alkyl sulfate ion, halogen ion and p-toluenesulfonate ion, and more preferable from the viewpoint of ease of production of the dispersant (2). Is an alkyl sulfate ion, more preferably a methyl sulfate ion.
It is speculated that the structural unit derived from (2A) is present in the dispersant (2) as a form of structural unit derived from (meth) acryloylaminoalkyltrimethylammonium salt or (meth) acryloylaminoalkyltriethylammonium salt by quaternization. Is done. In this specification, (meth) acryloyl means at least one selected from acryloyl and methacryloyl.
Further, the dispersant (2) may be obtained by copolymerizing the ammonium salt monomer as (2C).

<Alkoxy polyalkylene glycol (meth) acrylate (2B)>
In the alkoxypolyalkylene glycol (meth) acrylate (2B), the polyalkylene glycol portion preferably includes a structural unit derived from propylene oxide (hereinafter also referred to as “PO”), more preferably a structural unit derived from propylene oxide and It includes structural units derived from ethylene oxide (hereinafter also referred to as “EO”).
(2B) is preferably an alkoxy polyalkylene glycol methacrylate. In the present specification, “(meth) acrylate” means at least one selected from acrylate and methacrylate.

In addition, the content of the structural unit derived from EO in the polyalkylene glycol moiety [(a structural unit derived from PO) / (a structural unit derived from EO + a structural unit derived from PO) × 100] is determined by dispersibility, dispersion stability, and solvent From the viewpoint of improving dispersibility, it is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and still more preferably 60% by mass or more, from the viewpoint of ease of production of the dispersant. Preferably, it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less.
The polyalkylene glycol moiety may be either a block adduct or a random adduct, but is preferably a block adduct from the viewpoint of enhancing the dispersibility of the pigment in an organic solvent, and more preferably the methacrylate side is derived from EO. The adduct is a block adduct whose terminal side is a structural unit derived from PO.
Such an alkoxy polyalkylene glycol (meth) acrylate can be obtained, for example, by the following method. By starting with aliphatic alcohol or the like as a starting material, PO is polymerized in the presence of a base catalyst, and then EO is polymerized to obtain alkoxy polypropylene glycol polyethylene glycol. Furthermore, the alkoxy polyalkylene glycol (meth) acrylate (2B) is obtained by dehydrating the alkoxy polypropylene glycol polyethylene glycol and (meth) acrylic acid.

From the viewpoint of the contrast ratio, the average number of moles of alkylene oxide added to the polyalkylene glycol moiety (2B) is preferably 20 or more, more preferably 30 or more, and from the viewpoint of ease of production of (2B), Preferably it is 200 or less, More preferably, it is 150 or less, More preferably, it is 50 or less.
(2B) has 1 or more carbon atoms in the alkoxy group, preferably 6 or more, more preferably 8 or more, and preferably 22 or less, more preferably 18 or less, from the viewpoint of contrast ratio. .
Preferred examples of the alkoxy group include a methoxy group, an ethoxy group, an octoxy group, a lauroxy group, a myristyloxy group, a stearyloxy group, and an oleyloxy group.

The content of the structural unit derived from (2B) in all the structural units of the dispersant (2) is preferably 51% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass from the viewpoint of the contrast ratio. As described above, it is more preferably 75% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. In addition, let said content be the conversion mass which excluded the mass of the component derived from a quaternizing agent.

<Production of Dispersant (2)>
The dispersant (2) can be prepared by, for example, a method of copolymerizing a mixture of (Method 1) (2A), (2B) and (2C) by a known polymerization method, or (Method 2) (2A) and (2B) can be obtained by a method comprising a step of obtaining a copolymer and a step of treating the copolymer with a quaternizing agent. From the viewpoint of the ease of production of the dispersant (2) and the contrast ratio, (Method 2) is preferred.

Hereinafter, (Method 2) will be described in detail.
The polymerization method for copolymerizing (2A) and (2B) is preferably a solution polymerization method.
The solvent used in the solution polymerization method is preferably an ether solvent described later from the viewpoint of ease of production of the pigment dispersion and the colored composition.
The ether solvent is preferably (poly) alkylene glycol monoalkyl ether acetate, more preferably at least one selected from PGMEA and BCA, and further preferably PGMEA.

In the polymerization, a polymerization initiator or a polymerization chain transfer agent can be used. As the polymerization initiator, 2,2′-azobis (2,4-dimethylvaleronitrile) is preferable, and the polymerization chain transfer agent is used. Is preferably 2-mercaptoethanol.
Although preferable polymerization conditions vary depending on the type of polymerization initiator and the like, the polymerization temperature is preferably 50 to 80 ° C., and the polymerization time is preferably 1 to 20 hours. The polymerization atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon.

The step of treating with a quaternizing agent to obtain a dispersant is performed by reacting the quaternizing agent with the copolymer of dialkylaminoalkyl (meth) acrylamide and alkoxypolyalkylene glycol (meth) acrylate obtained in the above step. To do.
As the quaternizing agent, a substance that reacts with a tertiary amino group to convert the amino group to quaternary ammonium is used. For example, dialkyl sulfate such as dimethyl sulfate or diethyl sulfate; halogenation such as methyl chloride or methyl iodide Alkyl; aryl halides such as benzyl chloride; alkyl p-toluenesulfonates such as methyl p-toluenesulfonate and ethyl p-toluenesulfonate. From the viewpoint of reactivity, dimethyl sulfate is preferred.
The quaternization rate can be adjusted by adjusting the addition molar ratio of the quaternizing agent to the copolymer.

<Other dispersants>
Other dispersants used in the present invention include, for example, commercially available products manufactured by BYK Chemie, trade names: Dispersic P104, Dispersic P104S, Dispersic 220S, Dispersic 110, Dispersic 111, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 164, Dispersic 166, Dispersic 170, Dispersic 171, Dispersic 174, Dispersic 2000, Dispersic 2095; trade names: EFKA 4300, EFKA 5010, EFKA 5065, EFKA 5066, EFKA 5070, EFKA 7500, EFKA 7554; manufactured by Lubrizol, trade name: Sol Sparse 3000, Solsperse 16000, Solsperse 17000, Solsperse 28000, Solsperse 36000, Solsperse 36600, Solsperse 41000, Solsperse 76500; manufactured by Kawaken Fine Chemical Co., Ltd., trade name: Hinoact KF-1000; Ajimoto Fine Techno Co., Ltd. PB822, Ajisper PB881 etc. are mentioned.

[solvent]
The solvent used in the present invention is preferably a non-aqueous solvent, more preferably an ether solvent, and still more preferably a glycol ether solvent.
The viscosity of the solvent at 25 ° C. is preferably 0.8 to 5.0 mPa · s, more preferably 0.9 to 4.0 mPa · s, and still more preferably 1.0 to 3 from the viewpoint of improving the contrast ratio. .5 mPa · s.
The SP value of the solvent is preferably 7 from the viewpoint of increasing the affinity with the pigment surface, low surface tension, compatibility with the binder component used in the color filter, etc., and improving the contrast ratio of the resulting cured film. 0.5 to 10.5, more preferably 8.0 to 9.5, and still more preferably 8.5 to 9.0. The SP value is determined by the method of Fedors [Robert F. Fedors, Polymer Engineering and Science, 14, 147-154 (1974)].
The boiling point of the solvent is preferably 50 to 300 ° C., more preferably 100 to 260 ° C., and still more preferably 120 to 200 ° C., from the viewpoint of easy removal by coating film drying and work safety.

The glycol ether solvent is preferably (poly) alkylene glycol monoalkyl ether acetate, (poly) alkylene glycol monoalkyl ether propionate and (poly) alkylene glycol dialkyl ether, more preferably from the viewpoint of increasing luminance and contrast ratio. Is (poly) alkylene glycol monoalkyl ether acetate. In the present specification, “(poly) alkylene glycol” means at least one selected from alkylene glycol and polyalkylene glycol.
Examples of (poly) alkylene glycol monoalkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, diethylene glycol Examples include monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate (BCA). Among these, from the viewpoints of pigment dispersibility, contrast ratio, and brightness improvement, PGMEA (boiling point: 146 ° C., viscosity at 25 ° C .: 1.1 mPa · s, SP value: 8.73) and BCA (boiling point: 247) are preferable. Viscosity at 25 ° C .: 3.1 mPa · s, SP value: 8.94), more preferably PGMEA.

[Rhodamine dye]
The coloring composition for a color filter of the present invention preferably contains a rhodamine dye from the viewpoint of dispersion stability.
The rhodamine dye used in the present invention preferably has two or more of at least one selected from the functional groups represented by formula (RIa) and formula (RIb).
-SO ₃ H (RIa)
-SO ₃ ^- (RIb)
[The counter ion of the anion group represented by the formula (RIb) is one selected from a metal ion, NH ₄ ⁺ and an iminium cation of the rhodamine dye. ]
From the viewpoint of dispersion characteristics, the total number of functional groups contained in one molecule of rhodamine dye is 2 or more, preferably 4 or less, more preferably 3 or less, and still more preferably 2. .
The functional group is preferably bonded to the aromatic ring in the rhodamine molecular skeleton or the aromatic ring carbon bonded to the rhodamine molecular skeleton.
The rhodamine dye preferably has a functional group represented by the formula (RIa) and the formula (RIb), and the counter ion of the anion group represented by the formula (RIb) is at least one selected from a metal ion and NH ₄ ⁺ It is.
The rhodamine dye preferably has a functional group represented by the formula (RIb), more preferably a functional group represented by the formula (RIb), and a counter ion of the anion group represented by the formula (RIb). Has a functional group which is a metal ion.
Examples of the metal ion include Na ⁺ , K ^{+ and the} like, and Na ⁺ is preferable from the viewpoint of luminance and availability.

Preferred examples of the rhodamine dye include compounds represented by the following general formula (RI).

[In the formula (RI), R ¹¹ to R ¹⁴ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a functional group represented by the formula (RIa) or the formula (RIb), and hydrogen. atom is a substitutable aromatic hydrocarbon group, R ^15, R ¹⁶ each independently represent a hydrogen atom, a functional group represented by the formula (RIa) or formula (RIb). However, in formula (RI), the total number of functional groups represented by formula (RIa) or formula (RIb) is 2 or more. ]

The number of carbon atoms of the aliphatic hydrocarbon group of R ¹¹ to R ¹⁴ is preferably 1 or more from the viewpoint of luminance, preferably 10 or less, more preferably 6 or less, still more preferably 4 or less, Even more preferred is 2.
The number of carbon atoms of the aromatic hydrocarbon group of R ¹¹ to R ¹⁴ is preferably 6 or more, preferably 18 or less, more preferably 14 or less, still more preferably 10 or less, from the viewpoint of luminance. Is more preferably 8.
The suitable aspect and total number of the functional group represented by a formula (RIa) or a formula (RIb) are as above-mentioned.
The rhodamine dye is preferably at least one selected from compounds represented by the following formulas (RI-1) to (RI-3) from the viewpoints of luminance and dispersion stability.

Commercially available rhodamine dyes include C.I. I. Acid Red 50 ("Sulforhodamine G" manufactured by Sigma-Aldrich), C.I. I. Acid Red 52 (hereinafter also referred to as “AR52”) (“AR52” manufactured by Daiwa Kasei Co., Ltd .: compound of formula (I-1)), in which —SO ₃ Na of AR52 is replaced with —SO ₃ H ( (Hereinafter also referred to as “AR52-H”) (“Daiwa IJ Red 207H” manufactured by Daiwa Kasei Co., Ltd .: compound of formula (I-2)), C.I. I. Acid Red 289 (hereinafter also referred to as “AR289”) (“AR289” manufactured by Daiwa Kasei Co., Ltd .: compound of formula (I-3)), in which —SO ₃ Na in AR289 is replaced with —SO ₃ H ( Daiwa Kasei Co., Ltd. product "Daiwa IJ Red 319H") etc. are mentioned. Among these, from the viewpoint of luminance and dispersion stability, it is preferably at least one selected from AR52, AR52-H and AR289, and from the viewpoint of luminance, more preferably at least selected from AR52 and AR52-H. One type, more preferably AR52.

[Aromatic compound having two or more maleimide groups]
The colored composition for a color filter of the present invention preferably contains an aromatic compound having two or more maleimide groups (hereinafter also referred to as “maleimide compound”) from the viewpoint of heat resistance.
The maleimide compound is used to improve the heat resistance of the cured film by preventing the pigment from sublimation when the colored composition is cured and then exposed to high temperature conditions.
The maleimide compound used in the present invention has at least one aromatic ring.
Examples of maleimide compounds include 1,3-phenylene dimaleimide, 1,4-phenylene dimaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4′-diphenylsulfone bismaleimide, bis- (3-ethyl- And at least one selected from 5-methyl-4-maleimidophenyl) methane and 2,2-bis- [4- (4-maleimidophenoxy) phenyl] propane.
From the viewpoint of solubility in a solvent and from the viewpoint of improving heat resistance and substrate adhesion, phenylene dimaleimide is preferred, and N, N′-1,3-phenylene dimaleimide (hereinafter referred to as “PDM”) is more preferred. It is also referred to as “

[Alkali-soluble resin]
The coloring composition for a color filter of the present invention preferably contains an alkali-soluble resin. The alkali-soluble resin is used for dissolving an unexposed portion in a developer when a color filter is produced by a photolithography method.
As the alkali-soluble resin, those generally used for negative resists can be used, and those having solubility in an alkaline aqueous solution, that is, 1% by mass in a 0.05% by mass tetramethylammonium hydroxide aqueous solution at 20 ° C. There is no particular limitation as long as it dissolves as described above.
Examples of the alkali-soluble resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl ( (Meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) Chryrate, 1-adamantyl (meth) acrylate, allyl (meth) acrylate, 2,2'-oxybis (methylene) bis-2-propenoate, styrene, γ-methylstyrene, 2-hydroxyethyl (meth) acrylate, 2-dimethyl At least one selected from aminoethyl (meth) acrylate, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, and glycidyl (meth) acrylate; Examples include a copolymer comprising at least one selected from acrylic acid, methacrylic acid, dimer of acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid and anhydrides thereof. it can.
Examples thereof include a polymer obtained by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the above copolymer. Among these, a polymer having an ethylenically unsaturated bond, which is obtained by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to a copolymer, is a polyfunctional monomer described later at the time of exposure. Polymerization is possible, and the colored layer is particularly stable in that it is more stable. Commercially available products of such alkali-soluble resins include “ACRYCURE RD-KA-501”, “RD-KA-502”, “BX-KA-01” and “BK-KA-02” manufactured by Nippon Shokubai Co., Ltd. “M6100”, “M7100”, “M8030”, etc. of “Aronix” series manufactured by Toagosei Co., Ltd. can be mentioned.
The weight average molecular weight of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, from the viewpoint of curability of the coating film, and preferably 50,000 or less, from the viewpoint of developability. More preferably, it is 40,000 or less.
Among the above, as the alkali-soluble resin used in the present invention, a copolymer of (meth) acrylic acid ester and (meth) acrylic acid is preferably used. In the present specification, “(meth) acrylic acid” means at least one selected from acrylic acid and methacrylic acid.
Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, and Examples thereof include at least one selected from benzyl (meth) acrylate. Among these, benzyl methacrylate and methyl (meth) acrylate are preferable. That is, the copolymer of (meth) acrylic acid ester and (meth) acrylic acid is preferably a copolymer of benzyl (meth) acrylate and (meth) acrylic acid, or methyl (meth) acrylate and (meth) acrylic. At least one selected from a copolymer with an acid, more preferably a copolymer of benzyl methacrylate and methacrylate.
The copolymerization ratio (molar ratio) of (meth) acrylic acid ester and (meth) acrylic acid is preferably 90/10 to 50/50, more preferably 80/20 to 60/40.

[Polyfunctional monomer]
It is preferable that the coloring composition for color filters of this invention contains a polyfunctional monomer. The polyfunctional monomer is used for curing the exposed portion when producing a color filter by a photolithography method. As polyfunctional monomer, (meth) acrylic acid ester (for example, dipentaerythritol hexaacrylate) having two or more ethylenically unsaturated double bonds, urethane (meth) acrylate, (meth) acrylic acid amide, allyl compound Vinyl ester and the like, preferably dipentaerythritol hexaacrylate (hereinafter also referred to as “DPHA”).

[Photopolymerization initiator]
The colored composition for a color filter of the present invention preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include at least one selected from aromatic ketones, lophine dimers, benzoin, benzoin ethers, and polyhalogens. Preferably, a combination of 4,4′-bis (diethylamino) benzophenone and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 4- [pN, N-di (ethoxycarbonylmethyl)- 2,6-di (trichloromethyl) -s-triazine] and 2-methyl-4 ′-(methylthio) -2-morpholinopropiophenone, more preferably 2-methyl-4 '-(Methylthio) -2-morpholinopropiophenone (hereinafter also referred to as “MMTMPP”).

[Production Method of Colored Composition]
The colored composition of the present invention can be obtained, for example, by a production method having the following steps (1) and (2).
Step (1): Dispersing a mixture containing a pigment containing compound (a) and compound (b), a dispersant, a solvent, optionally a rhodamine dye, optionally a maleimide compound, and optionally an alkali-soluble resin. Step (2) for obtaining a pigment dispersion by mixing the pigment dispersion obtained in the step (1), a polyfunctional monomer, and a photopolymerization initiator to obtain a colored composition

<Step (1)>
Various known dispersers can be used as the mixing disperser used for dispersion. Examples thereof include high-speed stirring and mixing devices such as homomixers, kneaders such as roll mills, kneaders and extruders, high-pressure dispersers such as high-pressure homogenizers, media-type dispersers such as paint shakers and bead mills. These devices can be used in combination.
Among these, from the viewpoint of uniformly mixing the pigment in the solvent, a high-speed stirring and mixing apparatus such as a homomixer, and a media type dispersing machine such as a paint shaker or a bead mill are preferable. Examples of commercially available media type dispersers include “Ultra Apex Mill” manufactured by Kotobuki Industries Co., Ltd. and “Picomill” manufactured by Asada Tekko Co., Ltd.
In the case of using a media type disperser, the material of the media used in the dispersion step is preferably a ceramic material such as zirconia or titania, a polymer material such as polyethylene or nylon, a metal, or the like, and zirconia is preferred from the viewpoint of wear. Further, the diameter of the media is preferably 0.003 mm or more, more preferably 0.01 mm or more, and preferably 0.5 mm or less, more preferably 0, from the viewpoint of crushing the aggregated particles in the pigment. 4 mm or less.
The dispersion time is preferably 0.3 hours or more, more preferably 1 hour or more from the viewpoint of sufficiently miniaturizing the pigment, and preferably 200 hours or less, from the viewpoint of the production efficiency of the pigment dispersion. Preferably it is 50 hours or less.

The dispersion method in the dispersion step of the present production method may obtain the desired dispersion by one dispersion of the mixture, but after the mixture is predispersed using a medium, further than the preliminary dispersion step. The main dispersion is preferably performed using a small medium from the viewpoint of obtaining a finer and more uniform pigment dispersion.

(Preliminary dispersion)
As the mixing and dispersing machine used in the preliminary dispersion, the above-described various dispersing machines can be used. From the viewpoint of uniformly mixing the pigment into the solvent, a media type dispersing machine such as a paint shaker or a bead mill is preferable.
The diameter of the media used in the preliminary dispersion step is preferably 0.1 mm or more, preferably 0.5 mm or less, more preferably 0.4 mm or less, from the viewpoint of crushing the aggregated particles in the pigment. is there.
The dispersion time in the preliminary dispersion step is preferably 0.1 hour or more, more preferably 0.5 hour or more, and still more preferably 1 hour or more from the viewpoint of crushing the aggregated particles in the pigment. From the viewpoint of body production efficiency, it is preferably 10 hours or less, more preferably 5 hours or less, and even more preferably 4 hours or less.

(Distributed)
This dispersion is a process of dispersing the preliminary dispersion obtained in the preliminary dispersion, and is performed to further refine the mixture obtained in the preliminary dispersion process. From the viewpoint of refining the pigment, It is preferable to use a type disperser, and the above-described high pressure type disperser may be used in combination.
The diameter of the media used in this dispersion step is preferably less than 0.1 mm, more preferably 0.08 mm or less, and even more preferably 0.07 mm or less from the viewpoint of making the pigment finer. From the viewpoint of separation, it is preferably 0.003 mm or more, more preferably 0.01 mm or more.
The dispersion time of this dispersion is preferably 2 hours or more, more preferably 3 hours or more from the viewpoint of sufficiently miniaturizing the pigment, and preferably 200 hours or less from the viewpoint of the production efficiency of the pigment dispersion. More preferably, it is 50 hours or less, More preferably, it is 24 hours or less.
In addition, the preferable range of the compounding quantity of each component in a process (1) is the same as the following <composition of a pigment dispersion>.

<Composition of pigment dispersion>
The content of the pigment in the pigment dispersion is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 12% by mass or more, from the viewpoint of obtaining good colorability. It is 30 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 16 mass% or less.
From the viewpoint of improving the contrast ratio, the mass ratio of the dispersant to the pigment in the pigment dispersion [dispersant / pigment] is preferably 0.2 or more, more preferably 0.3 or more, and still more preferably 0.4 or more. Moreover, it is preferably 1.5 or less, more preferably 1.2 or less, and still more preferably 0.9 or less.
The content of the solvent in the pigment dispersion is preferably 20% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more, from the viewpoint of reducing the viscosity of the dispersion. It is 95 mass% or less, More preferably, it is 90 mass% or less.
The content of the rhodamine dye in the pigment dispersion is preferably 0.05% by mass or more, more preferably 0.5% by mass or more, based on the total amount of the pigment and the rhodamine dye, from the viewpoint of luminance and dispersion characteristics. Further, it is preferably 2.0% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass from the viewpoint of suppressing the dissolution of the rhodamine dye in the non-aqueous solvent and maintaining the dispersion stability. Hereinafter, from the viewpoint of increasing luminance in addition to the above viewpoint, it is more preferably 10% by mass or less, and still more preferably 5% by mass or less.
The content of the maleimide compound in the pigment dispersion is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more based on the pigment from the viewpoint of heat resistance. Further, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
From the viewpoint of heat resistance, the total content of the dispersant and the maleimide compound in the pigment dispersion is preferably 2% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more with respect to the pigment. Moreover, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
From the viewpoint of dispersibility, the content of the alkali-soluble resin in the pigment dispersion is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, and still more preferably 3.5% by mass. % Or less, preferably 0% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more.

<Step (2)>
In step (2), an alkali-soluble resin may be further blended.
In this step, they may be added in any order, and a polyfunctional monomer or the like may be added to the pigment dispersion, or a pigment dispersion may be added to the polyfunctional monomer or the like. The mixing method is not particularly limited, and a colored composition for a color filter can be obtained by stirring with a stirring device or the like.

[Coloring composition for color filter]
The content of the pigment in the color filter coloring composition is preferably 4% by mass or more, more preferably 5% by mass or more, and preferably 10% by mass or less, from the viewpoint of obtaining good colorability. Preferably it is 8 mass% or less.
The content of the solvent in the coloring composition is preferably 60% by mass or more, more preferably 70% by mass or more, and preferably 90% by mass or less, more preferably, from the viewpoint of obtaining good colorability and viscosity. Is 85 mass% or less.
The content of the rhodamine dye in the coloring composition is preferably 0.05% by mass or more, more preferably 0.5% by mass or more, based on the total amount of the pigment and the rhodamine dye, from the viewpoint of luminance and dispersion characteristics. Further, it is preferably 2.0% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass from the viewpoint of suppressing the dissolution of the rhodamine dye in the non-aqueous solvent and maintaining the dispersion stability. Hereinafter, from the viewpoint of increasing luminance in addition to the above viewpoint, it is more preferably 10% by mass or less, and still more preferably 5% by mass or less.
The content of the alkali-soluble resin in the coloring composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more from the viewpoint of obtaining good developability and film hardness. In addition, it is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.
The content of the polyfunctional monomer in the coloring composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 2% by mass or more from the viewpoint of obtaining good film hardness. Moreover, it is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 4% by mass or less.
The content of the photopolymerization initiator in the coloring composition is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, more preferably 1.5% by mass from the viewpoint of obtaining good film hardness. Further, it is preferably 10% by mass or less, more preferably 7.0% by mass or less, and still more preferably 4.0% by mass or less.
The amount of the maleimide compound in the coloring composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more with respect to the pigment from the viewpoint of improving heat resistance. Moreover, it is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.

[Usage]
The coloring composition for a color filter of the present invention is used for producing a color filter.
The color filter manufacturing method preferably has the following steps (a) and (b).
Step (a): A step of applying a colored composition of the present invention on a substrate, photocuring and developing to obtain a coating film Step (b): The coating film obtained in the above step (a) at 200 to 300 ° C. The process of obtaining a cured film by heating

The coating in the step (a) is preferably performed on a glass substrate by a roll coater, slit coater, spray, bar coater, applicator, spin coater, dip coater, inkjet, or screen printing. After coating, it is preferable to remove the solvent and heat from the viewpoint of smoothness of the coating film and handling. The heating temperature is preferably 50 to 140 ° C, more preferably 70 to 90 ° C. The heating time is preferably 0.5 to 60 minutes, more preferably 1 to 10 minutes.
In photocuring, the coating film is irradiated with ultraviolet rays, and the polyfunctional monomer in the coloring composition undergoes a crosslinking reaction to cure the coating film. Photocuring is performed to leave a pattern on the glass substrate in the subsequent development, and it is preferable not to cure the portion removed by development by placing a photomask for preventing ultraviolet rays. The photocuring is preferably performed until the ultraviolet irradiation amount is 10 to 100 mJ / cm ² .
In the development, the cured coating film after photocuring is immersed in an alkaline aqueous solution and rinsed with water to remove uncured portions. The alkaline aqueous solution used preferably has an alkali agent concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. The alkaline agent used for development is preferably an aqueous solution of ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, triethanolamine, tetramethylammonium hydroxide, etc. More preferred.
The pH of the alkaline aqueous solution is preferably 10.0 to 13.0.

Step (b) is a step of obtaining a cured film by heating the coating film obtained in step (a) to 200 to 300 ° C. Step (b) is a post-baking step, and by performing this step, a cured film having excellent hardness can be formed.
From the viewpoint of obtaining a cured film having excellent hardness and optical properties, the heating temperature is preferably 210 to 280 ° C, more preferably 220 to 270 ° C. From the same viewpoint, the heating time is preferably 5 to 120 minutes, more preferably 10 to 40 minutes.
The heat resistance in the step (b) can be enhanced by using the coloring composition for a color filter of the present invention.

In relation to the above-described embodiment, the present invention further discloses the following color composition for color filter, color filter, method for producing color filter, pigment composition and the like.
<1> A compound containing a pigment, a dispersant, and a solvent, wherein the pigment contains a compound (a) represented by the general formula (Ia) and a compound (b) represented by the general formula (Ib), The coloring composition for color filters whose content of compound (b) is 3 mol% or more and 90 mol% or less with respect to the sum total of a) and compound (b).

<2> The colored composition for a color filter according to <1>, wherein the substitution position on the phenyl group of two bromine atoms in the compound (a) is a para position.
<3> The colored composition for a color filter according to <1> or <2>, wherein the substitution position on the phenyl group of two chlorine atoms in the compound (b) is a para position.
<4> The content of the compound (b) with respect to the sum of the compound (a) and the compound (b) is preferably 6 mol% or more, more preferably 12 mol% or more, still more preferably 15 mol% or more, and even more preferably 17 mol. % Or more, preferably 83 mol% or less, more preferably 78 mol% or less, still more preferably 58 mol% or less, still more preferably 40 mol% or less, still more preferably 35 mol% or less, still more preferably 30 mol% or less. The coloring composition for a color filter according to any one of <1> to <3>, more preferably 25 mol% or less, and still more preferably 20 mol% or less.
<5> The content of the compound (b) with respect to the total of the compound (a) and the compound (b) is more preferably 26 mol% or more, still more preferably 45 mol% or more, and preferably 83 mol% or less. The colored composition for a color filter according to any one of <1> to <3>, more preferably 78 mol% or less, and still more preferably 58 mol% or less.
<6> The content of the diketopyrrolopyrrole pigment containing the compound (a) and the compound (b) in the pigment is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more. More preferably, it is 60% by mass or more, and from the viewpoint of optimizing color characteristics, it is preferably 100% by mass or less, more preferably 90% by mass or less, according to any one of <1> to <5>. Coloring composition for color filter.
<7> The total content of the compound (a) and the compound (b) in the diketopyrrolopyrrole pigment is preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more. The coloring composition for a color filter according to any one of <1> to <6>, which is preferably 100% by mass or less, more preferably 95% by mass or less.
<8> As a pigment other than the diketopyrrolopyrrole pigment, preferably at least one selected from an azo pigment, a condensed polycyclic pigment, and a lake pigment, more preferably a condensed polycyclic pigment, and still more preferably an anthraquinone pigment , Still more preferably C.I. I. The coloring composition for a color filter according to any one of <1> to <7>, further containing CI Pigment Red 177.
<9> The content of the pigment other than the diketopyrrolopyrrole pigment is, for example, 0% by mass or more, preferably 10% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably. Is a coloring composition for a color filter according to <8>, which is 50% by mass or less, more preferably 40% by mass or less.

<10> The colored composition for a color filter according to any one of <1> to <9>, wherein the dispersant preferably has a cationic group.
<11> The color filter according to <10>, wherein the cationic group is preferably at least one selected from a quaternary ammonium group and an ammonium group (—NH ₃ ⁺ ), preferably a quaternary ammonium group. Coloring composition.
<12> The colored composition for a color filter according to any one of <1> to <11>, wherein the dispersant preferably has a polyalkylene oxide chain, and more preferably has a polyalkylene oxide chain as a side chain.
<13> The colored composition for a color filter according to any one of <1> to <12>, wherein the dispersant is preferably a polymer dispersant.
<14> The colored composition for a color filter according to any one of <1> to <13>, wherein the dispersant preferably has a cationic group in the main chain.
<15> The weight average molecular weight of the dispersant is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, still more preferably 3,500 or more, and preferably 35. The coloring composition for a color filter according to any one of <1> to <14>, wherein the coloring composition is 10,000 or less, more preferably 20,000 or less, and still more preferably 10,000 or less.

<16> The SP value of the solvent is preferably 7.5 to 10.5, more preferably 8.0 to 9.5, still more preferably 8.5 to 9.0, <1> to <15> The coloring composition for color filters in any one of.
<17> The color filter colorant according to any one of <1> to <16>, wherein the solvent has a boiling point of preferably 50 to 300 ° C, more preferably 100 to 260 ° C, and still more preferably 120 to 200 ° C. Composition.
<18> The solvent is preferably a non-aqueous solvent, more preferably an ether solvent, more preferably a glycol ether solvent, still more preferably selected from propylene glycol monomethyl ether acetate (PGMEA) and diethylene glycol monobutyl ether acetate (BCA). The coloring composition for color filters according to any one of <1> to <17>, wherein the coloring composition is at least one selected from the group consisting of PGMEA.

<19> The colored composition for a color filter according to any one of <1> to <18>, preferably further containing a rhodamine dye.
<20> The colored composition for a color filter according to any one of <1> to <19>, preferably further containing an aromatic compound having two or more maleimide groups.
<21> The colored composition for a color filter according to any one of <1> to <20>, preferably further containing an alkali-soluble resin.
<22> The colored composition for a color filter according to any one of <1> to <21>, preferably further containing a polyfunctional monomer.
<23> The colored composition for a color filter according to any one of <1> to <22>, preferably further containing a photopolymerization initiator.

<24> The content of the pigment in the colored composition is preferably 4% by mass or more, more preferably 5% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less. The coloring composition for a color filter according to any one of <1> to <23>.
<25> The content of the rhodamine dye in the coloring composition is preferably 0.05% by mass or more, more preferably 0.5% by mass or more, and further preferably 2%, based on the total amount of the pigment and the rhodamine dye. 0.01% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and still more preferably 5% by mass or less. <1> to <24 > The coloring composition for color filters in any one of>.
<26> The content of the solvent in the colored composition is preferably 60% by mass or more, more preferably 70% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less. The coloring composition for a color filter according to any one of <1> to <25>.
<27> The content of the alkali-soluble resin in the colored composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 20% by mass. The color filter coloring composition according to any one of <1> to <26>, which is more preferably 15% by mass or less, and still more preferably 10% by mass or less.
<28> The content of the polyfunctional monomer in the coloring composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 2% by mass or more, and preferably 10%. The coloring composition for a color filter according to any one of <1> to <27>, which is not more than mass%, more preferably not more than 5 mass%, still more preferably not more than 4 mass%.
<29> The content of the photopolymerization initiator in the colored composition is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, more preferably 1.5% by mass or more. The colored composition for a color filter according to any one of <1> to <28>, which is preferably 10% by mass or less, more preferably 7.0% by mass or less, and still more preferably 4.0% by mass or less.
<30> The amount of the maleimide compound in the coloring composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and preferably with respect to the pigment. The colored composition for a color filter according to any one of <1> to <29>, which is 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

<31> A method for producing a colored composition for a color filter, comprising the following steps (1) and (2).
Step (1): Dispersing a mixture containing the compound (a) represented by the general formula (Ia) and the pigment (1) represented by the general formula (Ib), a dispersant, and a solvent Step (2) for obtaining a pigment dispersion by mixing the pigment dispersion obtained in Step (1), a polyfunctional monomer, and a photopolymerization initiator to obtain a colored composition <32> Step The production method according to <31>, wherein the mixture of (1) preferably further contains a rhodamine dye.
<33> The production method according to <31> or <32>, wherein the mixture in the step (1) preferably further contains an alkali-soluble resin.
<34> The method according to any one of <31> to <33>, wherein the mixture of step (1) preferably further contains a maleimide compound.

<35> A method for producing a color filter, comprising the following steps (a) and (b).
Step (a): A step of applying a colored composition of the present invention on a substrate, photocuring and developing to obtain a coating film Step (b): The coating film obtained in the above step (a) at 200 to 300 ° C. The process of obtaining a cured film by heating

<36> Compound (a) represented by general formula (Ia) and compound (b) represented by general formula (Ib), and a compound ( The pigment composition whose content of b) is 3 mol% or more and 90 mol% or less.

<37> Use of the pigment composition according to <36> for producing a color filter.
<38> Use of the colored composition according to any one of <1> to <30> for the production of a color filter.

In the following production examples, examples and comparative examples, X in the notation “alkylene glycol (X)” means the average number of moles of alkylene oxide added to the alkylene glycol. In addition, the average addition mole number of PO and EO in the alkoxypolyalkylene glycol, the weight average molecular weight, the solid content, the reaction rate measurement, the confirmation of the quaternization reaction, the contrast ratio of the cured film obtained from the colored composition, the luminance, the heat resistance The evaluation of the properties and the measurement of the base amount and the acid amount of the pigment were carried out by the following methods.

(1) Measurement of average addition mole number of PO and EO in alkoxy polyalkylene glycol Sample obtained by esterifying terminal hydroxyl group of alkoxy polyalkylene glycol with trifluoroacetic acid using NMR measurement apparatus (“Mercury 400 type” manufactured by Varian). proton nuclear magnetic resonance ⁽¹ H-NMR) was determined from the spectrum (measurement conditions: non decoupling method, relaxation time of 10 seconds, integrated number 32 times). A solution in which 0.01 g of a sample treated with trifluoroacetic acid was dissolved in 0.99 g of deuterated chloroform was used for measurement. The average added moles of PO and EO were calculated by the following formulas, respectively.
PO average addition mole number = (integral value of signal derived from methyl group of polyoxypropylene) / (integral value of signal derived from methylene group adjacent to trifluoroacetate group) /1.5
EO average added mole number = (integral value of signal derived from methylene group of polyoxyethylene) / (integral value of signal derived from methylene group adjacent to trifluoroacetate group) / 2

(2) Measurement of weight average molecular weight The weight average molecular weight was measured under the following conditions using gel permeation chromatography (hereinafter also referred to as “GPC”).
The measurement sample was prepared as follows. The amount of the solid content of the solution containing the compound obtained in the below-mentioned production example is 0.05 g in a glass bottle ("Screw tube No. 5" manufactured by Maruem Co., Ltd.), and the total amount is obtained by adding the following eluent. 10 g and sealed. Subsequently, the glass bottle was stirred at 2500 rpm for 1 minute using a test tube mixer (“Minishaker MS1” manufactured by IKA), and 100 μL of the resulting solution was used as a measurement sample.
<Condition 1>
GPC [apparatus: manufactured by Tosoh Corp. “HLC-8320GPC”, detector: differential refractometer (attached to the device), column: “TSK-GEL, α-M” x 2 manufactured by Tosoh Corporation, flow rate: 0.6 mL / min, column temperature: 40 ° C.) Was measured using the following polyethylene glycol as a standard substance.
[Standard material: Polyethylene glycol]
“2070-1 (Mw 106)”, “2070-3 (Mw 400)”, “2070-6 (Mw 1500)”, “2070-8 (Mw 6450)” manufactured by GL Sciences Inc .; “SE-” manufactured by Tosoh Corporation 5 (Mw 45000) ";" PEOX270K (Mw 258000) "," PEOX1000K (Mw 992000) "manufactured by American Polymer Standards Corp.
<Condition 2>
GPC (apparatus: “HLC-8220GPC” manufactured by Tosoh Corporation, detector), using as an eluent a solution obtained by dissolving dimethyldodecylamine (“Farmin DM20” manufactured by Kao Corporation) at 100 mmol / L in chloroform. A differential refractometer (attached to the apparatus), column: “K-804L” manufactured by Showa Denko KK, flow rate: 1.0 mL / min, column temperature: 40 ° C.] was measured using the following polystyrene as a standard substance.
[Standard material: Polystyrene]
“A-500 (Mw 590)”, “A-5000 (Mw 5060)”, “F-2 (Mw 18100)”, “F-10 (Mw 96400)”, “F-40 (Mw) manufactured by Tosoh Corporation 427000) "; manufactured by pressure chemical" PS30908 (Mw 50000) "

(3) Measurement of solid content 10 g of dry anhydrous sodium sulfate and a glass rod were placed in a petri dish, 2 g of a sample was weighed, mixed with a glass rod, and dried for 2 hours with a 105 ° C. vacuum dryer (pressure 8 kPa). The mass after drying was measured, and the solid content was calculated from the following formula.
Solid content (mass%) = [(mass after drying g) − (Petri dish + glass rod + mass g of dry anhydrous sodium sulfate)] / (mass g of sample) × 100

(4) Measurement of reaction rate (based on the ratio of chloride ion content)
Since the chlorine of the alkoxypolyalkylene glycol monochloroacetate becomes chloride ion by the reaction, the reaction rate based on the ratio of chloride ion amount was calculated from the following equation.
Reaction rate (%) = [chloride ion amount (mass%)] / [total chlorine content (mass%)] × 100
The chloride ion content was determined by the Volhard method, and the total chlorine content was determined by the Volhard method after decomposition with sodium butyrate.
(Amine reduction standard)
Since the reaction turns the amine into a quaternary salt and the amine value decreases, the reaction rate based on the amount of amine decrease was calculated from the following equation.
Reaction rate (%) = [(amine value before reaction mg / KOH) − (amine value after reaction mg / KOH)] / (amine value before reaction mg / KOH) × 100
The amine value was a value obtained by converting the amount of perchloric acid required for neutralization into KOH.

(5) Confirmation of Quaternization Reaction Proton nuclear magnetic resonance ( ¹ H-NMR) of raw material amine compound, halogenated alkyl ester compound and quaternized product using NMR measuring apparatus (“Mercury 400 type” manufactured by Varian). The spectrum was obtained (measurement conditions: non-decoupling method, relaxation time 10 seconds, number of integrations 32 times). A solution obtained by dissolving 0.01 g of a sample in 0.99 g of deuterated chloroform was used for the measurement.

(6) Evaluation of contrast ratio and brightness The colored compositions obtained in Examples and Comparative Examples were applied on a glass substrate with a spin coater, and then allowed to stand for 50 minutes on a horizontal table to obtain a coated substrate. Using a UV fiber spot irradiation device ("MUV-202U" manufactured by Moritex Co., Ltd.), the coating film substrate was irradiated with UV light at 40 mJ / cm ² and further heated in a clean oven at 230 ° C for 20 minutes to obtain a cured film substrate. Got. Using this cured film substrate as a sample, the contrast ratio was measured with a contrast ratio measuring device (“CT-1” manufactured by Aisaka Electric Co., Ltd.).
Using the cured film substrate, chromaticity coordinates (Y, x, y) were measured with a chromaticity meter (Nippon Denshoku Industries Co., Ltd. “SE-6000”). The value of chromaticity coordinate Y was evaluated as luminance.
The larger the contrast ratio value, the better. The larger the value of Y, the better the brightness.

(7) Evaluation of heat resistance of cured film A photomask is placed on the coated substrate obtained in the above “(6) Evaluation of contrast ratio and brightness”, and an ultraviolet fiber spot irradiation device (“MUV-202U” manufactured by Moritex Corporation). ) Was irradiated with ultraviolet rays at 40 mJ / cm ² to obtain an exposed substrate. This exposed substrate is slowly swung in a 0.1% by weight aqueous solution of tetramethylammonium hydroxide, pulled up from the aqueous solution in 5 second increments, and when an exposure pattern appears, uncured portions are removed with running water, and further at 250 ° C. A development substrate was obtained by heating for a minute. Using an optical microscope adjusted to an observation magnification of 500 times (“VHX-500” manufactured by Keyence Corporation, lens: “VH-Z500”), the major axis of 0.1 is observed on and around the exposure pattern on the development substrate. The number of acicular crystal-like foreign matters of ˜15 μm was counted in the range of 300 μm × 200 μm. The smaller the number of foreign substances, the better the heat resistance.

(8) Measurement of pigment base amount and acid amount 1) Base amount Weigh accurately 2 g of pigment (sample amount), and add 0.1 mL of 0.1N hydrochloric acid aqueous solution and 2-butanone / ion-exchanged water (mass ratio 11/89) 54 mL. In addition to the above mixed solution, the mixture was stirred at 400 r / min for 1 hour using a stirrer chip and a magnetic stirrer (“REXIM RS-4DN” manufactured by ASONE). The obtained suspension was centrifuged at 15000 r / min for 120 minutes using a centrifuge (“3K30C” manufactured by Kubota Corporation), and 30 mL of the obtained liquid phase part was added to 20 mL of ion-exchanged water. The solution was neutralized with 1N aqueous sodium hydroxide. The amount of base was calculated from the following equation using BmL as the titration amount of the aqueous sodium hydroxide solution required for neutralization and Sg as the sample amount.
Base amount (μmol / g) = 100 × (3-B) / S

2) Acid amount 2 g of pigment is precisely weighed (sample amount) and added to a mixed solution of 6 mL of 0.1N sodium hydroxide aqueous solution and 54 mL of 2-butanone / ion-exchanged water (mass ratio 11/89). The mixture was stirred at 400 r / min for 1 hour using a tic stirrer (“REXIM RS-4DN” manufactured by ASONE). The obtained suspension was centrifuged at 15000 r / min for 120 minutes using a centrifuge (“3K30C” manufactured by Kubota Corporation), and 30 mL of the obtained liquid phase part was added to 20 mL of ion-exchanged water. Neutralization titration with 1N aqueous hydrochloric acid. The amount of acid was calculated from the following equation, where the titration amount of the aqueous hydrochloric acid solution required for neutralization was AmL and the sample amount was Sg.
Acid amount (μmol / g) = 100 × (3-A) / S

Production Example 1 [Synthesis of Lauroxy Polypropylene Glycol (29) Polyethylene Glycol (15)]
A 6.0 L autoclave equipped with a stirrer and a temperature controller was used as a reaction apparatus. 375 g (2.0 mol) of lauryl alcohol (“Kalcoal 2098” manufactured by Kao Corporation) and 12.4 g of a 48 mass% potassium hydroxide aqueous solution were charged, and the atmosphere was replaced with nitrogen. Dehydration was performed at 100 ° C. and 4.7 kPa for 1.0 hour, and the pressure was returned to atmospheric pressure with nitrogen. PO addition reaction was performed at 110 ° C. for 36 hours while introducing 3694 g (63.6 mol) of PO at a pressure of 0.1 to 0.45 MPa. Subsequently, EO addition reaction was carried out at 140 ° C. for 12 hours while introducing 1405 g (31.9 mol) of EO at a pressure of 0.1 to 0.4 MPa. After cooling to 60 ° C., 5.3 g of glacial acetic acid (manufactured by Kishida Chemical Co., Ltd., special grade reagent) was added and stirred for 1 hour. Lauroxy polypropylene glycol (29) polyethylene glycol (15) (hereinafter referred to as “lauroxy PPG ( 29) PEG (15) ”was also obtained.

Production Example 2 [Synthesis of Lauroxy PPG (29) PEG (15) Methacrylate]
500 g (0.21 mol) of Lauroxy PPG (29) PEG (15) obtained in Production Example 1 was added to a 1 liter four-necked flask equipped with a stirrer, thermometer, air blowing tube, Dean-Stark tube, and Dimroth tube. ), 360 g of toluene, 12.3 g of p-toluenesulfonic acid monohydrate, and 0.6 g of hydroquinone were heated to 50 ° C. and stirred at 50 to 60 ° C. for 30 minutes. Thereafter, 22.5 g (0.29 mol) of methacrylic acid was added, and the mixture was reacted at 110 to 120 ° C. for 9 hours while blowing air through a blowing tube. After cooling to 50-60 ° C., the mixture was transferred to a separatory funnel, 5N aqueous sodium hydroxide solution was added, and the mixture was shaken well, and the lower layer produced after standing was separated. Furthermore, 20 mass% sodium chloride aqueous solution was added and shaken well, and the lower layer produced after standing was separated. Further, the operation of adding a 20% by mass aqueous sodium chloride solution and shaking well and separating the lower layer produced after standing was repeated until the pH of the lower layer reached 7-8. To the upper layer, 0.05 g of p-methoxyphenol was added, and toluene was removed at 60 ° C. under reduced pressure to obtain Lauroxy PPG (29) PEG (15) methacrylate.

Production Example 3 [Synthesis of Lauroxy PPG (29) PEG (15) Monochloroacetate]
In a 3 liter four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube, and cooling tube, 653 g of Lauroxy PPG (29) PEG (15) obtained in Production Example 1 and monochloroacetic acid (Wako Pure Chemical Industries, Ltd.) 35.1 g (manufactured by Co., Ltd., special grade reagent) and 3.5 g of p-toluenesulfonic acid monohydrate (manufactured by Kishida Chemical Co., Ltd., special grade reagent) were charged, and nitrogen substitution was performed while stirring. . The temperature was raised to 140 ° C., and the reaction was allowed to proceed for 16 hours while reducing pressure (10 kPa) using a vacuum pump (“BSW-50” manufactured by Sato Vacuum Machinery Co., Ltd.) connected to a cooling pipe while blowing nitrogen. After the temperature was lowered to 80 ° C., 26.8 g of anhydrous sodium carbonate (manufactured by Kishida Chemical Co., Ltd., special grade reagent) was added and stirred for 2 hours. The obtained liquid was filtered with a filter paper (“No. 5A” manufactured by Advantech Toyo Co., Ltd.) to obtain Lauroxy PPG (29) PEG (15) Monochloroacetate.

Production Example 4 [Synthesis of Dispersant 1 (N, N, N ′, N′-tetramethylpropanediamine quaternized product by Lauroxy PPG (29) PEG (15) Monochloroacetate)]
In a separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirring device, 254 g of Lauroxy PPG (29) PEG (15) monochloroacetate obtained in Production Example 3, N, N, N ′, N ′ -6.4 g of tetramethylpropanediamine ("Kaoriza No. 2" manufactured by Kao Corporation) was charged, and nitrogen substitution was performed. The reaction was allowed to proceed for 20 hours while stirring at 80 ° C. 385 g of PGMEA was added, stirred for 1 hour, cooled, and dispersion 1 (N, N, N ′, N′-tetramethylpropanediamine quaternized product with Lauroxy PPG (29) PEG (15) monochloroacetate) A PGMEA solution was obtained. The solid content of the solution was 39.4% by mass, and the weight average molecular weight was 4000 (measured value according to <Condition 1>). The reaction rate obtained from the ratio of the chloride ion content to the total chlorine content was 93 mol%, and the reaction rate obtained from the amine reduction amount was 99 mol%. According to the NMR measurement results, signals derived from the methyl group and methylene group bonded to N of N, N, N ′, N′-tetramethylpropanediamine were 2.2, 2.3 ppm to 3.0, respectively, depending on the reaction. At 4.0 ppm, the signal derived from the methylene group one further away from N shifted from 1.6 ppm to 2.8 ppm. In addition, the signal derived from the methylene group to which chlorine of Lauroxy PPG (29) PEG (15) monochloroacetate was bonded shifted from 4.1 ppm to 4.9 ppm by the reaction.

Production Example 5 [Dispersant 2 (3- (N, N-dimethylamino) propylacrylamide / lauroxy PPG (29) PEG (15) methacrylate copolymer (17.5 / 82.5 mass%) and its quaternized product] ; Synthesis of quaternization rate 32 mol%)
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer, 10.6 g of 3- (N, N-dimethylamino) propylacrylamide (DMAPAA)), lauroxy PPG obtained in Production Example 2 ( 29) PEG (15) methacrylate 49.6 g, 2-mercaptoethanol (manufactured by Toyobo Co., Ltd., hereinafter referred to as “ME”) 0.36 g and PGMEA 90 g were added, and the inside of the reaction vessel was stirred and replaced with nitrogen. . After the temperature in the reaction vessel was increased to 78 ° C. with stirring, a separately prepared monomer solution [DMAPAA 24.6 g, Lauroxy PPG (29) PEG (15) methacrylate 115.6 g, ME 0.84 g, PGMEA 210 g, 2, 2-azobis- (2,4-dimethylvaleronitrile) (“V-65” (hereinafter also referred to as “V-65”) 4.0 g) manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise over 3 hours. Thereafter, a solution in which 0.5 g of V-65 was dissolved in 2.0 g of PGMEA was added and stirring was continued for 1 hour, and then a solution in which 0.5 g of V-65 was dissolved in 2.0 g of PGMEA was further added and stirred. This was continued for 1 hour and cooled to obtain a PGMEA solution of the pre-quaternization dispersant 2. The solid content of the solution was 40.3% by mass, and the pre-quaternization dispersant 2 had a weight average molecular weight of 14500 ( Was a condition measured value by 2>).
Next, 100 g of the solution was put in a glass container, and nitrogen substitution was performed. To this, 9.2 g of a 20 mass% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 15 minutes while stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of the dispersant 2 (DMAPAA / lauroxy PPG (29) PEG (15) methacrylate copolymer quaternized product). The solid content of the solution was 38.9% by mass, and the quaternization rate was 32 mol% of DMAPAA before quaternization.

Production Example 6 [Compound (a): Synthesis of Brominated Diketopyrrolopyrrole (Pigment a)]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux tube, 244 g of tert-amyl alcohol and 31 g of metallic sodium were reacted at 120 ° C. in a nitrogen atmosphere to prepare an alcoholate solution. To the alcoholate solution heated to 80 ° C., 152.5 g of tert-amyl alcohol, 127.4 g of 4-bromobenzonitrile, and 99.5 g of di-tert-amyl succinate were added. The mixture was stirred for a time to obtain a precursor. A mixture of 700 g of methanol, 1000 g of water, and 68.9 g of sulfuric acid was cooled to −10 ° C., the precursor was added, and the mixture was stirred for 3 hours while maintaining the liquid temperature at −5 ° C. to complete the reaction. The obtained liquid was ultrafiltered to obtain a solid content, and water and methanol were used, and the washing of the solid content was repeated until the filtrate was not colored and no salt was precipitated. Thereafter, the solid content was dried in a vacuum dryer at 80 ° C. for 24 hours and pulverized to obtain 150 g of brominated diketopyrrolopyrrole (pigment a).

Production Example 7 [Preparation of PR177 dispersion (dispersion P)]
PR177 (“Chromofine Red 6130EC” manufactured by Dainichi Seika Co., Ltd.) 19.5 g, N, N′-1,3-phenylene dimaleimide (PDM) 1.0 g, PGMEA 94.9 g, obtained in Production Example 4 Dispersant 1 solution 34.6g (solid content 13.6g) and zirconia beads 300g with a particle size of 0.3mm were placed in a 500mL plastic container and dispersed by a disperser ("Paint Shaker" manufactured by Asada Tekko Co., Ltd.) (Dispersion) was performed for 3 hours, and zirconia beads were removed by filtration. 100 g of the obtained liquid and 200 g of zirconia beads having a particle diameter of 0.05 mm were placed in a 250 mL plastic container, dispersed (mainly dispersed) by the disperser for 12 hours, zirconia beads were removed by filtration, and PR177 was 13 A PR177 dispersion (dispersion P) containing 9.8% by mass of a total of 9.8% by mass of the dispersant and the PDM was obtained.

Production Example 8 [Synthesis of alkali-soluble resin (benzyl methacrylate / methacrylic acid copolymer)]
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube and a thermometer, 12.0 g of methacrylic acid (hereinafter also referred to as “MAA”), 28.0 g of benzyl methacrylate (hereinafter also referred to as “BzMA”), 0.56 g of 3-mercaptopropionic acid and 40 g of PGMEA were added, and nitrogen substitution was performed while stirring the reaction vessel. The temperature in the reaction vessel was raised to 78 ° C. with stirring, and then a separately prepared monomer solution [MAA 48.0 g, BzMA 112.0 g, 3-mercaptopropionic acid 2.2 g, PGMEA 160 g, V-65 2.0 g] Was added dropwise over 3 hours. After completion of the dropwise addition, a solution prepared by dissolving 2.0 g of V-65 in 10.0 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, another solution of 1.0 g of V-65 dissolved in 10.0 g of PGMEA was added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution (alkali-soluble resin solution, hereinafter also referred to as “resin solution Q”) of a BzMA / MAA copolymer (molar ratio 7/3). The solid content of the solution was 50.0% by mass, and the weight average molecular weight of the BzMA-MAA copolymer was 14000 (measured value under <Condition 1>).

Example 1
(Preparation of pigment dispersion 1)
16.6 g (37.2 mmol) of pigment a obtained in Production Example 6 as the compound (a), PR254 (“HOSTAPER RED D2B-COF01” manufactured by Clariant Co., Ltd.) 2.9 g (8.1 mmol) as the compound (b) ), PDM 1.0 g, PGMEA 94.9 g, Dispersant 1 solution 34.6 g obtained in Production Example 4 (solid content 13.6 g), 0.3 mm particle size zirconia beads 300 g were put in a 500 mL plastic container, Dispersion (preliminary dispersion) with a disperser (“Paint Shaker” manufactured by Asada Tekko Co., Ltd.) was performed for 3 hours, and zirconia beads were removed by filtration. 100 g of the obtained liquid and 300 g of zirconia beads having a particle diameter of 0.05 mm are placed in a 250 mL plastic container, dispersed (mainly dispersed) by the disperser for 9 hours, and the zirconia beads are removed by filtration to obtain a pigment 13 A pigment dispersion 1 was obtained that contained 9.8% by mass of a total of 9.8% by mass of the dispersant and the PDM.
(Preparation of colored composition A1)
5.13 parts by mass of Pigment Dispersion 1, 0.74 parts by mass of the resin solution Q obtained in Production Example 8 (solid content: 0.37 parts by mass), dipentaerythritol hexaacrylate (DPHA) (polyfunctional monomer: Nippon Chemical Co., Ltd.) “DPHA” manufactured by Yakuhin Co., Ltd.) 0.26 parts by mass, 2-methyl-4 ′-(methylthio) -2-morpholinopropiophenone (MMTMPP) (photopolymerization initiator: manufactured by Wako Pure Chemical Industries, Ltd.) 0 20 parts by mass and 3.67 parts by mass of PGMEA were mixed until uniform to obtain a colored composition A1.
(Preparation of colored composition B1)
In order to evaluate the luminance (Y) at the same chromaticity (constant x value and y value), a coloring composition B1 containing PR177 was prepared as follows.
Pigment Dispersion 1 3.53 parts by mass, Dispersion P 1.60 parts by mass obtained in Production Example 7 containing PR177, 0.74 parts by mass of resin solution Q obtained in Production Example 8 (solid content 0. 37 parts by mass), 0.26 parts by mass of DPHA, 0.20 parts by mass of MMTMPP and 3.67 parts by mass of PGMEA were mixed until uniform to obtain a colored composition B1.

Examples 2 to 12, Comparative Examples 1 to 2 (Preparation of pigment dispersions 2 to 12, C1 to C2, coloring compositions A2 to A12, AC1 to AC2, B2 to B12, BC1 to BC2)
Pigment dispersions 2 to 12, C1 to C2, coloring compositions A2 to A12, AC1 to AC2, and coloring compositions B2 to B12 were prepared in the same manner as in Example 1, except that the amounts shown in Table 1 were used. BC1 to BC2 were obtained. In addition, the compound (b) used for preparation is as follows.
Pigment b1: PR254 “HOSTAPERM RED D2B-COF01” manufactured by Clariant (base amount: 43 μmol / g, acid amount: 42 μmol / g)
Pigment b2: PR254 “HOSTAPERM RED D2B-COFLV3781” manufactured by Clariant (base amount: 4 μmol / g, acid amount: 148 μmol / g)

Table 2 shows the evaluation results of the obtained colored compositions.

Claims

A pigment, a dispersant, and a solvent, wherein the pigment contains a compound (a) represented by the general formula (Ia) and a compound (b) represented by the general formula (Ib), The coloring composition for color filters whose content of compound (b) is 3 mol% or more and 90 mol% or less with respect to the sum total with compound (b).
The coloring composition for a color filter according to claim 1, wherein the content of the compound (b) with respect to the sum of the compound (a) and the compound (b) is 12 mol% or more and 40 mol% or less.
The coloring composition for a color filter according to claim 1 or 2, wherein the substitution position on the phenyl group of two bromine atoms is para-position in the compound (a).
The coloring composition for a color filter according to any one of claims 1 to 3, wherein the substitution position on the phenyl group of two chlorine atoms in the compound (b) is a para position.
The coloring composition for a color filter according to any one of claims 1 to 4, wherein the content of the diketopyrrolopyrrole pigment containing the compound (a) and the compound (b) in the pigment is 20% by mass or more and 100% by mass or less. object.
The coloring composition for a color filter according to any one of claims 1 to 5, wherein the total content of the compound (a) and the compound (b) in the diketopyrrolopyrrole pigment is 80% by mass or more and 100% by mass or less. .
The coloring composition for a color filter according to any one of claims 1 to 6, wherein the dispersant has a cationic group.
The coloring composition for a color filter according to claim 7, wherein the cationic group is a quaternary ammonium group.
The colored composition for a color filter according to any one of claims 1 to 8, wherein the dispersant has a polyalkylene oxide chain.
The colored composition for a color filter according to any one of claims 1 to 9, wherein the solvent is an ether solvent.
The colored composition for a color filter according to any one of claims 1 to 10, further comprising an aromatic compound having two or more maleimide groups.
The coloring composition for a color filter according to any one of claims 1 to 11, further comprising an anthraquinone pigment.
A color filter produced using the colored composition according to any one of claims 1 to 12.
The manufacturing method of a color filter which has the following processes (a) and (b).
Step (a): A step of applying the colored composition according to any one of claims 1 to 12 onto a substrate, photocuring and developing to obtain a coating film Step (b): Obtained in the step (a) The process of obtaining a cured film by heating the coating film to 200 to 300 ° C.
Containing compound (a) represented by general formula (Ia) and compound (b) represented by general formula (Ib), and the total of compound (a) and compound (b) A pigment composition having a content of 3 mol% or more and 90 mol% or less.
The pigment composition according to claim 15, wherein the content of the compound (b) with respect to the total of the compound (a) and the compound (b) is 12 mol% or more and 40 mol% or less.
Use of the pigment composition according to claim 15 or 16 for producing a color filter.
Use of the colored composition according to any one of claims 1 to 12 for producing a color filter.