JP7440016B2 - Dye dispersion composition for color filters and dye dispersion resist composition for color filters - Google Patents

Description

The present invention relates to a dye dispersion composition for color filters and a dye dispersion resist composition for color filters.

When Pigment Blue 15:6 and soluble dye are used together as a coloring agent in a color filter for organic EL, etc., the color development and brightness may be insufficient due to the influence of the manufacturing process. Furthermore, when a soluble dye is used in combination, there is a problem in that migration to other colors due to heat cannot be overcome.
Therefore, by using Pigment Blue 15:6 and an insoluble dye together as a coloring agent, reliability could be improved and the dispersion stability of the colorant could be ensured, but the brightness was insufficient.
Further, as described in Patent Documents 2 and 3, coloring compositions for color filters having dye particles with a small particle size are known, but anion, which is a counter ion of the dye, has not been made into fine particles. Moreover, since the dye itself is desalted to form a sulfonic acid group, it has at least solubility in each organic solvent. Furthermore, the viscosity change and optical properties were still insufficient.

Japanese Patent Application Publication No. 2010-211198 Japanese Patent Application Publication No. 2018-025612 Japanese Patent Application Publication No. 2018-025797

The problems to be solved by the present invention are to improve the dispersion stability of colorants when preparing a dye dispersion composition for color filters and a dye dispersion resist composition for color filters based on the composition; The goal is to achieve both high brightness. Another objective is to obtain a color filter whose contrast and color development do not change through the color filter manufacturing process.

［化１の構造式中、Ｒ^１～Ｒ^４は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基、又は置換基を有していてもよい炭素数６～１０の１価の芳香族炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－ＣＯ－又は－ＮＲ^１１－で置き換わっていてもよい。Ｒ^１及びＲ^２は、互いに結合して窒素原子と一緒になって窒素原子を含む環を形成してもよく、Ｒ^３及びＲ^４は、互いに結合して窒素原子と一緒になって窒素原子を含む環を形成してもよい。
Ｒ^５は、－ＯＨ、－ＳＯ_３ ^－、－ＳＯ_３Ｈ、－ＳＯ_３ ^－Ｚ^＋、－ＣＯ_２Ｈ、－ＣＯ_２ ^－Ｚ^＋、－ＣＯ_２Ｒ^８、－ＳＯ_３Ｒ^８又は－ＳＯ_２ＮＲ^９Ｒ^１０を表す。
Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又は炭素数１～６のアルキル基を表す。
ｍは、０～５の整数を表す。ｍが２以上のとき、複数のＲ^５は同一でも異なってもよい。
Ｘは、ハロゲン原子を表す。
Ｚ^＋は、Ｎ（Ｒ^１１）４^＋、Ｎａ^＋又はＫ^＋を表し、４つのＲ^１１は同一でも異なってもよい。
Ｒ^８は、炭素数１～２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｒ^９及びＲ^１０は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基を表し、該飽和脂肪族炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＮＨ－又は－ＮＲ^８－で置き換っていてもよく、Ｒ^９及びＲ^１０は、互いに結合して窒素原子と一緒に３～１０員含窒素複素環を形成していてもよい。
Ｒ^１１は、水素原子、炭素数１～２０の１価の飽和炭化水素基又は炭素数７～１０のアラルキル基を表す。］

［化２の構造式中、Ｒ^１～Ｒ^４及びＲ^６及びＲ^７は、上記化１における基と同じである。］
４．アクリル系ブロック重合体である分散剤に含まれるアミンが３級アミンまたは４級アミンである、２．又は３．に記載のカラーフィルター用染料分散組成物。
５．アクリル系ブロック重合体である分散剤のブロック重合体の分子中において、アミン部位が局在化されている１．～４．のいずれかに記載のカラーフィルター用染料分散組成物。
６．アルカリ可溶性樹脂の酸価が５～２５０ｍｇＫＯＨ／ｇである１．～５．のいずれかに記載のカラーフィルター用染料分散組成物。
７．１．～６．のいずれかに記載のカラーフィルター用染料分散組成物を含有するカラーフィルター用染料分散レジスト組成物。 In order to solve the above problems, the composition of a dye dispersion composition for color filters was studied in the present invention.
Therefore, the present invention consists of the following composition.
1. A dye dispersion composition for a color filter containing a micronized insoluble xanthene dye, a dispersant which is an acrylic block polymer, a dispersion aid which is a phenyl group-containing phosphoric acid, an alkali-soluble resin, and an organic solvent.
2. 1. The amine value of the dispersant, which is an acrylic block polymer, is 5 to 100 mgKOH/g. The dye dispersion composition for color filters described in .
3. 1. The micronized insoluble xanthene dye has the structure shown in the following chemical formula 1 and/or the following chemical formula 2. Or 2. The dye dispersion composition for color filters described in .

[In the structural formula of chemical formula 1, R¹～R⁴are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent monovalent hydrocarbon group having 6 to 10 carbon atoms which may have a substituent represents an aromatic hydrocarbon group, and -CH contained in the saturated hydrocarbon group₂- is -O-, -CO- or -NR¹¹- may be replaced. R¹and R²may be bonded to each other and together with a nitrogen atom to form a ring containing a nitrogen atom, and R³and R⁴may be bonded to each other and together with a nitrogen atom to form a ring containing a nitrogen atom.
R⁵is -OH, -SO₃ ^-,-SO₃H,-SO₃ ^-Z⁺,-CO₂H, -CO₂ ^-Z⁺,-CO₂R⁸,-SO₃R⁸or -SO₂N.R.⁹R¹⁰represents.
R⁶and R⁷each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer from 0 to 5. When m is 2 or more, multiple R⁵may be the same or different.
X represents a halogen atom.
Z⁺is N(R¹¹)4⁺, Na⁺or K⁺represents the four R¹¹may be the same or different.
R⁸represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R⁹and R¹⁰each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH contained in the saturated aliphatic hydrocarbon group₂- is -O-, -CO-, -NH- or -NR⁸- may be replaced with R⁹and R¹⁰may be bonded to each other to form a 3- to 10-membered nitrogen-containing heterocycle together with the nitrogen atom.
R¹¹represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

[In the structural formula of Chemical formula 2, R¹～R⁴and R⁶and R⁷is the same as the group in Formula 1 above. ]
4. 2. The amine contained in the dispersant, which is an acrylic block polymer, is a tertiary amine or a quaternary amine. Or 3. The dye dispersion composition for color filters described in .
5. 1. The amine moiety is localized in the molecule of the dispersant block polymer, which is an acrylic block polymer. ~4. The dye dispersion composition for color filters according to any one of the above.
6. 1. The alkali-soluble resin has an acid value of 5 to 250 mgKOH/g. ~5. The dye dispersion composition for color filters according to any one of the above.
7.1. ~6. A dye-dispersed resist composition for color filters, comprising the dye-dispersed composition for color filters according to any one of the above.

According to the present invention, the dispersion stability of the dye dispersion composition for color filters is improved, and when a dye dispersion resist composition for color filters is prepared based on the composition, the dye dispersion resist composition for color filters We were able to improve the brightness of objects and prevent changes in color tone during the manufacturing process.

Hereinafter, the dye dispersion composition for color filters and the dye dispersion resist composition for color filters of the present invention will be explained in detail.

The present invention mainly relates to a dye-dispersed composition for a color filter for a display device and a dye-dispersed resist composition for a color filter, particularly for a display device using an organic EL element. Further, the dye dispersion composition for color filters may be a composition other than a resist.
In any case, the dye dispersion composition for color filters of the present invention has excellent dispersion stability, and furthermore, when a dye dispersion resist composition for color filters is prepared, the dye dispersion resist composition for color filters has the following effect: It is possible to improve dispersion stability, improve brightness, and avoid discoloration during color filter manufacturing.
The present invention is a dye dispersion composition for color filters, and a dye dispersion resist composition for color filters, which is prepared by adding an alkali-soluble resin, a photopolymerizable compound, etc. to the dye dispersion composition for color filters.
The dye dispersion composition for color filters includes both photocurable and non-photocurable compositions.

[A. Composition of dye dispersion composition for color filter]
The dye dispersion composition for color filters of the present invention is mainly composed of an insoluble xanthene dye, a dispersion aid, an alkali-soluble resin, and an organic solvent, and may contain a block polymer as the dispersant and the alkali-soluble resin.

［化１の構造式中、Ｒ^１～Ｒ^４は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基、又は、置換基を有していてもよい炭素数６～１０の１価の芳香族炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－ＣＯ－又は－ＮＲ^１１－で置き換わっていてもよい。Ｒ^１及びＲ^２は、互いに結合して窒素原子と一緒になって窒素原子を含む環を形成してもよく、Ｒ^３及びＲ^４は、互いに結合して窒素原子と一緒になって窒素原子を含む環を形成してもよい。
Ｒ^５は、－ＯＨ、－ＳＯ_３ ^－、－ＳＯ_３Ｈ、－ＳＯ_３ ^－Ｚ^＋、－ＣＯ_２Ｈ、－ＣＯ_２ ^－Ｚ^＋、－ＣＯ_２Ｒ^８、－ＳＯ_３Ｒ^８又は－ＳＯ_２ＮＲ^９Ｒ^１０を表す。
Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又は炭素数１～６のアルキル基を表す。
ｍは、０～５の整数を表す。ｍが２以上のとき、複数のＲ^５は同一でも異なってもよい。
Ｘは、ハロゲン原子を表す。
Ｚ^＋は、Ｎ（Ｒ^１１）_４ ^＋、Ｎａ^＋又はＫ^＋を表し、４つのＲ^１１は同一でも異なってもよい。
Ｒ^８は、炭素数１～２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｒ^９及びＲ^１０は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基を表し、該飽和脂肪族炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＮＨ－又は－ＮＲ^８－で置き換っていてもよく、Ｒ^９及びＲ^１０は、互いに結合して窒素原子と一緒に３～１０員含窒素複素環を形成していてもよい。
Ｒ^１１は、水素原子、炭素数１～２０の１価の飽和炭化水素基又は炭素数７～１０のアラルキル基を表す。］
なおＸがハロゲン原子ではなく、リン原子や金属原子を含有する場合には、十分な保存安定性や光学特性を発揮できない可能性がある。 (Colored dye)
The dye that can be used in the present invention is a finely divided insoluble xanthene dye.
Insoluble xanthene dyes are dyes having a xanthene skeleton, and have the structure shown in Chemical Formula 1 below, and are insoluble in water, methanol, chloroform, toluene, NMP, dimethylacetamide, diacetone alcohol, PGMEA, and PGME. It is something. The solubility in any of these solvents is preferably less than 0.1% by weight, further preferably 0.05% by weight or less, more preferably 0.01% by weight or less, and most preferably 0.005% by weight or less. The combination with the solvent at this time makes it insoluble.
It is preferable that the insoluble xanthene dye has the structure shown in the following chemical formula 1 and/or the following chemical formula 2.

[In the structural formula of Chemical Formula 1, R ¹ to R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. -CH ₂ - contained in the saturated hydrocarbon group is -O-, -CO- or -NR ¹¹ -. May be replaced. R ¹ and R ² may be bonded to each other and combined with a nitrogen atom to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be bonded to each other and combined with a nitrogen atom to form a nitrogen atom-containing ring. You may form a ring containing
R ⁵ is -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ is represented.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ^5s may be the same or different.
X represents a halogen atom.
Z ⁺ represents N(R ¹¹ ) ₄ ⁺ , Na ⁺ or K ⁺ , and the four R ^11s may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and are included in the saturated aliphatic hydrocarbon group - CH ₂ - may be replaced with -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ are bonded to each other and together with the nitrogen atom, form a 3- to 10-membered It may form a nitrogen-containing heterocycle.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]
Note that if X contains a phosphorus atom or a metal atom instead of a halogen atom, sufficient storage stability and optical properties may not be exhibited.

［化２の構造式中、Ｒ^１～Ｒ^４及びＲ^６及びＲ^７は、上記化１における基と同じである。］

[In the structural formula of Chemical Formula 2, R ¹ to R ⁴ and R ⁶ and R ⁷ are the same as the groups in Chemical Formula 1 above. ]

In the dyes represented by Chemical Formulas 1 and 2 above, R ¹ and R ⁴ are phenyl groups optionally substituted with a methyl group and/or -SO ^3- , R ² and R ³ are hydrogen, R ⁵ is preferably SO ₃ ^- Z ⁺ or -SO ₃ ^- , more preferably Acid Red 289 or a product of Acid Red 289 treated with hydrochloric acid.

In the present invention, the micronized insoluble xanthene dye has a D50 of 0.040 to 0.050 μm, preferably a D10 of 0.020 to 0.030 μm, a D50 of 0.040 to 0.050 μm, and a D90 of 0. It has a distribution of .080 to 0.095 μm.
By employing a finely divided insoluble xanthene dye having such a particle size distribution, the stability and optical properties of a dye dispersion or a dye dispersion resist composition are affected.

Other dyes that may be used in combination include various dyes such as blue dye, green dye, red dye, yellow dye, purple dye, orange dye, and brown dye. Additionally, solvent dyes, acid dyes, direct dyes, etc. can be used. However, they can be used together as long as the effects of the present invention are not impaired.
Examples of these dyes are:

As a red dye, C. I. Solvent Red 25, 27, 30, 35, 49, 83, 89, 100, 122, 138, 149, 150, 160, 179, 218, 230; C.I. I. Direct Red 20, 37, 39, 44; C. I. Acid Red 6, 8, 9, 13, 14, 18, 26, 27, 51, 52, 87, 88, 89, 92, 94, 97, 111, 114, 115, 134, 145, 151, 154, 180, 183, 184, 186, 198; C. I. Basic Red 12 and 13; C. I. One or more of disperse threads 5, 7, 13, 17 and 58.

As a blue dye, C. I. Solvent Blue 5, 25, 35, 36, 37, 44, 45, 49, 59, 67, 70, 68, 78, 94; C.I. I. Direct Blue 25, 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; C. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 104, 112, 113, 120, 129, 138, 147, 150, 158, 161, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, 335, 340; C. I. Basic Blue 1, 3, 9, 25 and C. I. It is one or more types of Disperse Blue 198.

As a green dye, C. I. Acid Green 3, 9, 16 and C. I. It is one or more types of Basic Green 1 and 4.

As a yellow dye, C. I. Solvent Yellow 2, 5, 14, 15, 16, 19, 21, 33, 56, 62, 77, 83, 93, 104, 105, 114, 129, 130, 162; C.I. I. Disperse Yellow 3, 4, 7, 31, 54, 61, 201; C. I. Direct Yellow 1, 11, 12, 28; C. I. Acid Yellow 1, 3, 11, 17, 23, 38, 40, 42, 76, 98; C. I. It is one or more types of Basic Yellow 1.

As an orange dye, C. I. Solvent Orange 1, 2, 5, 6, 37, 45, 62, 99; C.I. I. Acid Orange 1, 7, 8, 10, 20, 24, 28, 33, 56, 74; C. I. Direct Orange 1 and C. I. It is one or more types of Disperse Orange 5.

As the purple dye, C. I. Solvent Violet 8, 9, 13, 14, 33, 36, 37, 45, 46, 47; C. I Disperse Violet 22, 24, 26, 28, C.I. I. Acid Violet 6B, 7, 9, 17, 19, 49, 66, C. I. Basic Violet 2, 7, 10; C. I. Direct Violet is one or more of 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, and 104.

In order to impart high brightness and contrast to the dye dispersion composition for color filters of the present invention, each of the above-mentioned dyes including the insoluble xanthene dye must be a finely divided dye as described above. By performing the microparticulation treatment, the maximum particle size of the insoluble dye can be reduced, and the primary particle size can be further made finer and more uniform.
In order to obtain this maximum particle size, a method may be adopted in which the dispersion of the insoluble xanthene dye is filtered through a filter having a corresponding pore size.
In the above-mentioned microparticulation treatment, an insoluble xanthene dye or the like is dissolved in a solvent in which an acid, a base, or the like is allowed to coexist as required. Solutes can be extracted from the solution by adding a solvent in which the insoluble xanthene dye is not soluble to the obtained solution to precipitate the insoluble xanthene dye, or by adding salt etc. to the obtained solution to perform salting out. Any known means that can extract the solid as a solid can be used. After that, a method can be adopted to obtain an insoluble xanthene dye or the like with a controlled maximum particle size by using a filter with a pore size that provides the required maximum particle size.
Another microparticulation treatment includes untreated dyes, water-soluble inorganic salts (sodium chloride, barium chloride, potassium chloride, etc., preferably sodium chloride, and the average particle size of the water-soluble inorganic salt used is (preferably 50 μm or less) and a water-soluble dispersion medium (alkoxy alcohols, glycols, ethers, etc.) that does not substantially dissolve the water-soluble inorganic salt. Lighter, sand mill, Trimix (trade name) manufactured by Inoue Seisakusho Co., Ltd., which is a planetary mixer described in JP-A-2006-192385, and Miracle, manufactured by Asada Tekko Co., Ltd., which is a continuous uniaxial kneading machine. After kneading with a kneading device such as KCK (trade name), salt milling is performed to remove the water-soluble inorganic salt and the water-soluble dispersion medium, warm water is added and stirred, and the mixture is washed with water and subjected to atomization treatment. It can be carried out.
Furthermore, from the viewpoint of suppressing the crystal growth of the dye and making it uniformly fine, it is preferable to carry out the fine particle treatment in the presence of the following dispersant and/or dispersion aid. The amount of dispersion aid used in this case is 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the dye.

(Dispersion aid)
The dispersion aid used in the dye dispersion composition for color filters of the present invention is a phosphonic acid having a phenyl group, such as monophenylphosphonic acid and diphenylphosphonic acid.
The amount of the dispersion aid used is 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the colored dye. If the content of the dispersion aid having an acid group is less than 0.5 parts by mass, the dye dispersion effect will decrease, while if it exceeds 30 parts by mass, the dye dispersion effect will not improve any further.

The method of using the above-mentioned dispersion aid having an acid group is as follows, for example.
(1) When using an insoluble dye that has been micronized in the absence of a dispersion aid that has acid groups, the dispersion that has acid groups per 100 parts by mass of the insoluble dye when dispersing the micronized insoluble dye The amount of auxiliary agent used is 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight.
(2) When using an insoluble dye that has been micronized in the presence of a dispersion aid having an acid group, add 0.5 to 30 parts by mass of the dispersion aid per 100 parts by mass of the insoluble dye during the micronization treatment of the insoluble dye. parts, preferably 1 to 10 parts by weight, and 0 to 29.5 parts by weight, preferably 0 parts by weight, of a dispersion aid having an acid group per 100 parts by weight of the insoluble dye when dispersing the micronized insoluble dye. ~12 parts by weight are used.
Note that the total amount of the dispersion aid having an acid group used during the micronization treatment and the amount of the dispersion aid having an acid group used during the dye dispersion of the insoluble dye after the micronization treatment is 100 mass of the insoluble dye. The dispersion aid having an acid group is used in an amount of 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight.

(dispersant)
The dye dispersion composition for color filters of the present invention contains a dispersant. This dispersant is an acrylic block polymer and can contain an amine compound and/or a pyridine ring-containing compound as a monomer. A block containing an amine compound and/or a pyridine ring-containing compound as a monomer may be localized in the molecule of the block polymer as an amine site and/or a pyridine ring site.
The amine value of the acrylic block polymer is preferably 5 to 100 mgKOH/g, more preferably 10 to 70 mgKOH/g. Further, 15 to 60 mgKOH/g is more preferable. In the present invention, the amine value refers to the mass (mg) of potassium hydroxide that is equivalent to the amount of hydrochloric acid required to neutralize 1 g of solid content of the resin, and the This is a value measured by a similar method.
In the dye dispersion composition for color filters of the present invention, the amount of the block polymer dispersant used is preferably 1 to 100 parts by mass, more preferably 1 to 100 parts by mass, based on 100 parts by mass of the insoluble dye. The amount is 10 to 80 parts by weight, more preferably 20 to 60 parts by weight. If the content of the dispersant is less than 1 part by mass, the dye dispersion effect will decrease, and the initial viscosity after preparation of the composition may increase, and the viscosity may increase significantly after storage, whereas if the content exceeds 100 parts by mass, In this case, the alkali developability may be deteriorated.
The types of blocks constituting the acrylic block polymer containing the above-mentioned amine compound monomer may be two or three or more types, and include the following.
One or more of the blocks may be a block containing a monomer having a radically polymerizable unsaturated bond, which is an amine compound.
The monomers constituting this block include acyclic amine compounds, heterocyclic amine compounds, or quaternary ammonium cation compounds as monomers containing amino groups, such as dimethylaminopropyl (meth)acrylate. , acyclic amine compounds such as dimethylaminoethyl (meth)acrylate, heterocyclic amine compounds such as pentamethylpiperidinyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate are quaternized and cationized with benzyl chloride. Preferred are quaternary ammonium cation compounds such as compounds such as pyridine ring-containing monomers, and compounds such as vinylpyridine as the pyridine ring-containing monomer. A block consisting of one type of monomer among these monomers may be used, a block formed by random polymerization of two or more types of monomers, or a block formed by block polymerization of two or more types of monomers. But it's okay.
Other polymerizable blocks copolymerized with blocks derived from monomers that are amine compounds may be blocks made of one type of monomer, or blocks formed by random polymerization of two or more types of monomers. But it's okay. It is preferable not to have a unit derived from a monomer containing an amino group or a pyridine ring. Further, it is more preferable that it does not contain a carboxylic acid group, a hydroxyl group, a thiol group, or a sulfur- or phosphorus-containing group. Note that the number of blocks made of other polymerizable ethylenically unsaturated monomers may be one or two types.
Other polymerizable ethylenically unsaturated monomers include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate, styrene, and 2-hydroxyethyl (meth)acrylate. Acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, glycerol (meth)acrylate such as glycerol monoacrylate, N-phenylmaleimide, polystyrene macromonomer, polymethylmethacrylate macromonomer, carboepoxy diacrylate Examples include copolymers with at least one ethylenically unsaturated monomer selected from the group of monomers and oligomers such as monomers and oligomers. However, it is preferable not to use N-vinylpyrrolidone, sulfur element-containing monomers, silicon-containing monomers, and fluorine-containing monomers.
As the block copolymer, a block resin synthesized by living radical polymerization or anionic polymerization can be used.
Examples of such dispersants include BYK-LP24074 and BYK-22906.

In addition to the block polymer dispersant used in the present invention, a conventional polymer dispersant having a basic group and conventionally used in the field of color filters can be used in combination. However, the content of the conventional polymer dispersant is within a range that does not impair the effects of the present invention.
Examples of such polymeric dispersants having a basic group include the following.
(1) Polyesters, polyamides, and polyesteramides having an amino group and/or imino group of a polyamine compound (e.g., poly(lower) alkylene amine such as polyallylamine, polyvinylamine, polyethylene polyimine, etc.) and a free carboxyl group. A reaction product with at least one member selected from the group consisting of:
(2) A carbodiimide compound having in its molecule at least one side chain selected from the group consisting of polyester side chains, polyether side chains, and polyacrylic side chains, and at least one basic nitrogen-containing group. .
(3) A reaction product of a low molecular weight amino compound such as poly(lower) alkyleneimine or methyliminobispropylamine and a polyester having a free carboxyl group.
(4) Polyesters having one hydroxyl group such as alcohols such as methoxypolyethylene glycol or caprolactone polyester in the isocyanate group of polyisocyanate compounds, compounds having 2 to 3 isocyanate group-reactive functional groups, isocyanate group-reactive A reaction product obtained by sequentially reacting aliphatic or heterocyclic hydrocarbon compounds having a functional group and a tertiary amino group.
(5) A reaction product obtained by reacting a polymer of acrylate having an alcoholic hydroxyl group with a polyisocyanate compound and a hydrocarbon compound having an amino group.
(6) A reaction product obtained by adding a polyether chain to a low molecular weight amino compound.
(7) A reaction product obtained by reacting a compound having an isocyanate group with a compound having an amino group.
(8) A reaction product obtained by reacting a polyepoxy compound with a linear polymer having a free carboxyl group and an organic amine compound having one secondary amino group.
(9) A reaction product of a polycarbonate compound having a functional group capable of reacting with an amino group at one end and a polyamine compound.
(10) selected from methacrylic esters or acrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, stearyl acrylate, benzyl acrylate, etc. at least one basic group-containing polymerizable monomer such as acrylamide, methacrylamide, N-methylolamide, vinylimidazole, vinylpyridine, a monomer having an amino group and a polycaprolactone skeleton, and styrene or a styrene derivative. , a copolymer with at least one other polymerizable monomer.
(11) Acrylic block copolymers, etc. consisting of a block having a basic group such as a tertiary amino group or a quaternary ammonium base and a block having no basic functional group.
(12) A dispersant obtained by subjecting polyallylamine to Michael addition reaction with a polycarbonate compound.
(13) A carbodiimide compound having at least one polybutadiene chain and at least one basic nitrogen-containing group.
(14) A carbodiimide compound having at least one side chain having an amide group and at least one basic nitrogen-containing group in the molecule.
(15) A polyurethane compound having a constitutional unit having an ethylene oxide chain and a propylene oxide chain, and having an amino group quaternized with a quaternizing agent.
(16) Obtained by reacting the isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule with the active hydrogen group of a compound having an active hydrogen group and a carbazole ring and/or azobenzene skeleton in the molecule. carbazole ring relative to the sum of the isocyanate group derived from an isocyanate compound having an isocyanurate ring and the urethane bond and urea bond generated by the reaction between the isocyanate group and the active hydrogen group in the molecule of the compound. and compounds containing 15 to 85% of azobenzene skeletons, etc.

(Alkali-soluble resin)
The dye dispersion composition for color filters of the present invention contains an alkali-soluble resin.
As the alkali-soluble resin, an alkali-soluble resin having a carboxyl group is preferable, and in particular, a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer is preferable. Combination is preferred.
Specifically, ethylenically unsaturated monomers having carboxyl groups such as acrylic acid and methacrylic acid, and styrene, methyl (meth)acrylate, and ethyl copolymerizable with ethylenically unsaturated monomers having carboxyl groups. (meth)acrylate, alkyl (meth)acrylate such as butyl (meth)acrylate, styrene, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, glycerol monoacrylate At least one ethylenically unsaturated monomer selected from the group of monomers and oligomers such as glycerol (meth)acrylate, N-phenylmaleimide, polystyrene macromonomer, polymethyl methacrylate macromonomer, carboepoxy diacrylate, etc. Examples include copolymers of

Such a resin acts as a binder for insoluble dyes and is soluble in the developer used in the development process when manufacturing color filters, particularly preferably in an alkaline developer. be.
Such alkali-soluble resin may be a random copolymer or a block copolymer. By employing a random copolymer, it is possible that the dye dispersion ability is improved more than other copolymers, and solubility in PGMEA and an alkaline developer can be imparted.
In particular, a copolymer consisting of an ethylenically unsaturated monomer having one or more carboxyl groups, such as a monomer consisting of (meth)acrylic acid or maleic acid, and another copolymerizable ethylenically unsaturated monomer. Combination is preferred.
The ethylenically unsaturated monomer having one or more carboxyl groups may be one type of monomer or two or more types of monomers. Preferably only methacrylic acid is used.
Other polymerizable ethylenically unsaturated monomers include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate, styrene, and 2-hydroxyethyl (meth)acrylate. , allyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, glycerol (meth)acrylate such as glycerol monoacrylate, N-phenylmaleimide, polystyrene macromonomer, polymethylmethacrylate macromonomer, hydroxyethyl (meth)acrylate Examples include copolymers with at least one ethylenically unsaturated monomer selected from the group of monomers and oligomers such as acrylate and carboepoxy diacrylate. Among them, it is preferable to employ benzyl methacrylate and hydroxyethyl methacrylate. However, it is preferable not to use N-vinylpyrrolidone or a sulfur element-containing monomer.
Examples of such alkali-soluble resins include Follett ZAH110 (manufactured by Soken Kagaku Co., Ltd.) and Follett ZAH115 (manufactured by Soken Kagaku Co., Ltd.).
Further, the alkali-soluble resin may have a photopolymerizable functional group.
Further, as the block copolymer, a block resin synthesized by living radical polymerization or anionic polymerization can be used.

The acid value of the alkali-soluble resin in the present invention is preferably 5 to 250 mgKOH/g, more preferably 50 to 200 mgKOH/g, and even more preferably 80 to 170 mgKOH/g from the viewpoint of development characteristics. In addition, in this invention, the said acid value is a theoretical acid value, and is a value calculated|required arithmetic based on the ethylenically unsaturated monomer which has a carboxyl group and its content.
Further, the weight average molecular weight of the alkali-soluble resin in the present invention is usually preferably from 1,000 to 100,000, more preferably from 3,000 to 50,000, from the viewpoint of development characteristics and solubility in organic solvents. , more preferably 7,000 to 20,000. In the present invention, the weight average molecular weight of the alkali-soluble resin is the weight average molecular weight in terms of polystyrene obtained based on GPC. In the present invention, Water 2690 (manufactured by Waters) is used as an apparatus, and PLgel 5 μm MIXED-D (manufactured by Agilent Technologies) is used as a column.
The amount of the alkali-soluble resin used in the present invention is preferably 1 to 200 parts by weight, more preferably 10 to 100 parts by weight, per 100 parts by weight of the insoluble dye used. In this case, if the amount of the alkali-soluble resin used is less than 1 part by mass, there is a risk that the development characteristics will deteriorate. On the other hand, if it exceeds 200 parts by mass, the concentration of the colorant decreases relatively, which may make it difficult to achieve the desired color concentration as a thin film.
Further, the alkali-soluble resin preferably does not contain any primary, secondary, or tertiary amino groups, and further does not contain quaternary ammonium groups. Furthermore, it is more preferable not to have a basic group.
Note that an alkali-soluble resin having a structure other than a block copolymer may be blended within a range that does not impair the effects of the present invention.

(Other resins)
As the resin used in the dye dispersion composition for color filters of the present invention, a resin having a transmittance of 80% or more, preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region can be used. As these resins, thermosetting resins, thermoplastic resins, alkali-soluble resins, and the following photopolymerizable compounds can be used.
Such a resin is preferably in the range of 5 to 94% by mass, more preferably 20 to 50% by mass in terms of the total amount of resins used, based on the total solid content of the dye dispersion composition for color filters. It is.
Examples of thermosetting resins and thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane. resins, phenolic resins, polyester resins, acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclized rubber, epoxy resins, celluloses, polybutadiene, polyimide resins, benzoguanamine resins, melamine resins, urea resins, etc. can be mentioned.
In addition, a photopolymerizable resin, which will be described later in the section of the dye-dispersed resist composition for color filters, may also be blended, if necessary.

(Organic solvent)
As the organic solvent used in the dye dispersion composition for color filters of the present invention, organic solvents conventionally used in the field of liquid crystal color filter resists can be suitably used. Specifically, ester-based organic solvents, ether-based organic solvents ^, ether ester-based organic solvents, ketone-based organic solvents, aromatic hydrocarbon-based These include organic solvents and nitrogen-containing organic solvents. If a large amount of organic solvent with a boiling point exceeding 220°C is contained, the organic solvent may not be sufficient when prebaking the dye dispersion composition for color filters or the coating film formed by applying the composition containing this composition. It may remain in the dried paint film without evaporating, resulting in a decrease in the heat resistance of the dry paint film. Furthermore, if a large amount of an organic solvent with a boiling point of less than 100° C. is contained, it becomes difficult to apply evenly and uniformly, and there is a possibility that a coating film with excellent surface smoothness cannot be obtained.

Specifically, the organic solvent used in the dye dispersion composition for color filters of the present invention includes ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Ether organic solvents such as monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , ether ester organic solvents such as ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, δ-butyrolactone; 2-hydroxy Methyl propionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ester organic solvents such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, and n-amyl formate; alcohol solvents such as methanol, ethanol, isopropyl alcohol, and butanol; N-methylpyrrolidone, Examples include nitrogen-containing organic solvents such as N,N-dimethylformamide and N,N-dimethylacetamide. These can be used alone or in combination of two or more.
Among these organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, -Heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, etc. are preferred, and propylene glycol is more preferred. Monomethyl ether acetate and propylene glycol monomethyl ether.

(barium sulfate)
Barium sulfate having a primary particle size of 5 to 20 nm can be used in the dye dispersion composition for color filters of the present invention in order to improve heat resistance (brightness).
The amount of barium sulfate used is in the range of 0 to 25 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the colored dye.
The above-mentioned barium sulfate is used during or after dispersing the colored dye that has been made into fine particles.

The dye dispersion composition for color filters of the present invention mainly consists of an insoluble dye, a dispersant, a dispersion aid, an alkali-soluble resin, and an organic solvent. It accounts for 90 to 100% by mass. As the dispersant, any of those mentioned above can be employed.
Moreover, the dye dispersion composition for color filters of the present invention can also be used as a resist composition without having photocurability.

(Additives that can be added as necessary)
Depending on the method for producing the dye dispersion composition for color filters, various additives such as photopolymerization initiators, thermal polymerization inhibitors, ultraviolet absorbers, and antioxidants can be used as appropriate. Examples of the photopolymerization initiator include those described below.

(Method for producing dye dispersion composition for color filters of the present invention)
A method for producing a dye dispersion composition for color filters using the above raw materials will be explained. Note that in the case of a dye-dispersed resist composition for a color filter that is not photocurable, it is not necessary to incorporate a photopolymerizable compound.
Therefore, first, a dye dispersion composition is prepared as described below.
A mixture consisting of a dye that has been micronized in the presence or absence of a dispersion aid, an alkali-soluble resin, a dispersant, an organic solvent, barium sulfate, and other additives as necessary is obtained. The obtained mixture is kneaded and dispersed using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic dispersion machine, and a high-pressure dispersion machine to obtain a dye dispersion composition.

When using multiple dyes together, the following method can be adopted.
(1) Obtain a dye dispersion composition for each dye in advance, mix these dye dispersion compositions in an arbitrary ratio, and then add resin, barium sulfate, organic solvent, and other additives as necessary. is added to produce the dye dispersion composition for color filters of the present invention.
(2) In advance, if necessary, a complementary color dye is mixed into the dye dispersion composition produced as described above in a predetermined ratio, and then resin, barium sulfate, and an organic solvent are added as necessary. , other additives are added to produce a dye dispersion composition, and dye dispersion compositions containing other dyes are produced in the same manner, and then the present invention is carried out through a step of mixing these. A dye dispersion composition for color filters is produced.
In addition, resin, barium sulfate, an organic solvent, and other additives are added as necessary to the dye dispersion composition for color filters obtained in (1) and (2), and a dye dispersion composition for color filters is prepared. may be prepared.
Next, a dye dispersion composition for a color filter can be obtained by mixing a complementary color dye to the prepared dye dispersion composition for a color filter at a predetermined ratio to the dye contained therein.

In the production methods (1) and (2) above, when using a micronized dye that has been micronized in the presence of a dispersion aid having acid groups, when dispersing the micronized dye, It is possible to produce it without containing any agent.
Furthermore, in the manufacturing methods (1) and (2) above, the resin and barium sulfate can be added during and/or after creating the dye dispersion composition.
In addition, among the manufacturing methods (1) and (2) above, it is preferable to use a dye that has been subjected to atomization treatment in the presence of a dispersion aid having an acid group, since it provides high tinting power and high brightness. preferable.

Currently, the main method for manufacturing color filters using dye-dispersed resist compositions for color filters is the photoresist method using a photocurable composition. The components contained in each of the photocurable dye dispersion composition for filters and the non-photocurable dye dispersion composition for color filters will be explained below.

[B. When the dye-dispersed resist composition for color filter is photocurable]
Next, the case where the dye-dispersed resist composition for color filters of the present invention is photocurable will be explained.
When the dye-dispersed resist composition for color filters of the present invention is photocurable, the composition has active energy ray curability and is an alkali-developable resist composition, and the dye, dispersant, and alkali-soluble resist composition are photocurable. It is mainly composed of a resin and an organic solvent, and further contains barium sulfate and a photopolymerizable compound.
The types and amounts of the dye, dispersant, resin other than the photopolymerizable compound, barium sulfate, and organic solvent are as described for the dye dispersion composition for color filters above.

Regarding the organic solvent, from the viewpoints of solubility of the alkali-soluble resin, dispersibility of the colored dye, coatability, etc., it is preferable that the amount of the organic solvent be 50% by mass or more in the dye-dispersed resist composition for color filters of the present invention. Preferably, it is more preferably contained in an amount of 70% by mass or more.

(Photopolymerizable compound)
The photopolymerizable compounds used in the dye-dispersed resist composition for color filters of the present invention include monomers, oligomers, photopolymerizable resins, etc. having one or more photopolymerizable unsaturated bonds in the molecule, and the above-mentioned color Use the same composition as described for the dye dispersion composition for filters. Monomers, oligomers, etc. that have photopolymerizable unsaturated bonds are those that polymerize due to the action of radicals and cations generated when the photopolymerization initiator described below is decomposed by active energy rays such as ultraviolet rays and electron beams. It has an unsaturated bond that can be turned into a resin.
Examples of photopolymerizable compounds having one photopolymerizable unsaturated bond in the molecule include alkyl methacrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. ; Aralkyl methacrylates or acrylates such as benzyl methacrylate and benzyl acrylate; Alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate; Aminoalkyl methacrylates such as N,N-dimethylaminoethyl methacrylate and N,N-dimethylaminoethyl acrylate or acrylate; methacrylic acid ester or acrylic acid ester of polyalkylene glycol alkyl ether such as diethylene glycol ethyl ether, triethylene glycol butyl ether, dipropylene glycol methyl ether; methacrylic acid ester of polyalkylene glycol aryl ether such as hexaethylene glycol phenyl ether; Examples include acrylic acid ester; isobornyl methacrylate or acrylate; glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate or acrylate.

Monomers having two or more photopolymerizable unsaturated bonds in the molecule as photopolymerizable compounds include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, and diethylene glycol dimethacrylate. , glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, di Pentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol Diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. It will be done. These monomers can be used alone or in combination of two or more.
Moreover, an oligomer obtained by polymerizing a photopolymerizable compound can be used.
As a photopolymerizable resin as a photopolymerizable compound, (meth) Resins into which photocrosslinkable groups have been introduced, such as acrylic compounds and cinnamic acid, are used. Half-esterify linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymers and α-olefin-maleic anhydride copolymers with (meth)acrylic compounds having hydroxyl groups such as hydroxyalkyl (meth)acrylates. Polymerized polymers are also used.
The photopolymerizable compounds capable of forming these resins can be used alone or in combination of two or more. In the present invention, the amount of the photopolymerizable compound used is preferably in the range of 3 to 50% by mass based on the total solid content in the dye-dispersed resist composition for color filters.

(Photopolymerization initiator)
The photopolymerization initiator used in the dye-dispersed resist composition for color filters of the present invention may be one that can generate radicals or cations when irradiated with active energy rays such as ultraviolet rays or electron beams. Not particularly limited, examples include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether , benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro- 2-Methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1[4-(methylthio)phenyl]-2 -morpholinopropan-1-one, triazine-based photopolymerization initiators, and the like. These photopolymerization initiators may be used alone or in combination of two or more. However, it may or may not contain an oxime ester photopolymerization initiator.
In the present invention, the content of the photopolymerization initiator is preferably in the range of 1 to 20% by mass based on the total solid content in the dye-dispersed resist composition for color filters.

The dye-dispersed resist composition for color filters of the present invention is mainly composed of a colored dye, a dispersion aid, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, barium sulfate, and an organic solvent. occupies a total of 90 to 100% by mass in the dye-dispersed resist composition for color filters.

(Additives that can be added as necessary)
When the dye-dispersed resist composition for color filters of the present invention is photocurable, various additives such as thermal polymerization inhibitors, ultraviolet absorbers, and antioxidants may be used as necessary. can.

[C. When the dye-dispersed resist composition for color filters is not photocurable]
When the dye-dispersed resist composition for color filters is not photocurable, the above B. When the dye dispersion resist composition for color filters is photocurable, it does not contain the photopolymerizable compound or photopolymerization initiator used, and if necessary, further explanation of the composition of the dye dispersion composition for color filters. Resins other than the photopolymerizable compounds shown in can be blended.

(Additives that can be added as necessary)
When the dye-dispersed resist composition for color filters of the present invention is not photocurable, various additives such as ultraviolet absorbers and antioxidants may be appropriately used as necessary.

(Method for producing dye-dispersed resist composition for color filters of the present invention)
A method for producing a dye-dispersed resist composition for color filters using the above materials will be explained. When the dye-dispersed resist composition for color filters is photocurable, the dye-dispersed resist composition for color filters obtained above is further combined with a photopolymerizable compound, a photopolymerization initiator, and, if necessary, an alkali-soluble one. A resin, barium sulfate, an organic solvent, and other additives are added to obtain the dye-dispersed resist composition for color filters of the present invention.
When it is not photocurable, the dye-dispersed resist composition for color filters of the present invention can be obtained by further adding any one of an alkali-soluble resin, barium sulfate, an organic solvent, and other additives. The same applies to the above manufacturing method.
In addition, as a method for producing a color filter using the dye dispersion composition for color filters of the present invention, a known means other than the dye dispersion composition, including the necessary equipment, is employed for production. can do.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. Note that unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass."

<Dye dispersion composition for color filter>
Dye dispersion compositions for color filters of Examples and Comparative Examples were obtained using the following materials.
(color material)
Desalted xanthene dye: 10 g of 1-methoxy-2-propanol was added to 2 g of Acid Red 289, and then 0.63 g of concentrated hydrochloric acid was added, followed by ultrasonication. The obtained solution was filtered using a 0.25 μm PTFE membrane filter. The obtained filtrate was added dropwise to 300 g of propylene glycol monomethyl ether acetate, and the precipitated chlorinated dye was filtered off. After drying, a hydrochloric acid-treated product of Acid Red 289 was obtained.
Micronized insoluble xanthene dye: A micronized insoluble xanthene dye obtained by the following micronization method.
Insoluble xanthene dye: Acid Red 289, which is not treated by the following micronization method.
Into a tank of a kneader (trade name: KHD-2, manufactured by Inoue Seisakusho), 10 parts by mass of the above desalted xanthene dye, 3 parts by mass of Acid Red 289, and 1.0 parts of dispersant 1 for micronization (composition below) were added. 5 parts by mass, 200 parts by mass of sodium chloride with a particle size of 20 μm, and 240 parts by mass of diethylene glycol were added, and the mixture was kneaded at 50° C. for 12 hours and salt milled. Next, 200 parts by mass of the obtained kneaded material was poured into 2 liters of warm water, and stirred for 1 hour while heating to 40° C. to form a slurry. After repeating filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 40°C to obtain 8.5 parts by mass of micronized insoluble xanthene dye.
(Composition of dispersant 1 for micronization: methyl methacrylate/butyl methacrylate/2-ethylhexyl methacrylate/benzyl methacrylate/dimethylaminoethyl methacrylate/=19/18/19/12/32 copolymer)

(dispersant)
BYK-LP24074 (manufactured by BYK Chemie)
(Solid content 45%, AB block structure, acrylic type, amine value 27mgKOH/g, acid value 15mgKOH/g)
BYK-22906 (manufactured by BYK Chemie)
(Solid content 40%, block structure, acrylic, amine value 50mgKOH/g)
DISPERBYK-167 (manufactured by BYK Chemie)
(Solid content 57%, block structure, polyester polyurethane type, amine value 13mgKOH/g)
Ajisper PB821 (manufactured by Ajinomoto Fine Chemicals)
(Solid content 100%, block structure, polyester polyamide type, amine value 10mgKOH/g)

(Dispersion aid)
Phenyl phosphoric acid Diphenyl phosphoric acid Acid Red 289

(Alkali-soluble resin)
Follet ZAH110 (manufactured by Soken Chemical Co., Ltd.) (solid content 35%)
Follet ZAH115 (manufactured by Soken Chemical Co., Ltd.) (solid content 35%)

(Organic solvent)
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

(Photopolymerizable compound)
DPHA: dipentaerythritol hexaacrylate (photopolymerization initiator)
Or907: 2-benzyl-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone, trade name Omnirad907, IGM Resins B. V. Company-made

(Manufacture of dye dispersion composition for color filter)
The above-mentioned micronized insoluble xanthene dye, or non-micronized insoluble xanthene dye, dispersant, dispersion aid, alkali-soluble resin, and solvent are mixed to have the composition shown in Table 1, and ready mill (bead diameter: 0.2 nm, filling rate 50%) for 60 minutes to obtain dye dispersion compositions for color filters of Examples 1 to 4 and Comparative Examples 1 to 5.

(D50 particle size)
The particle size of the dye dispersion composition was measured by a laser diffraction particle size measurement method.
Measurement was performed based on the volume average particle diameter measured with a measuring device: Nanotrack (UPA-EX150, manufactured by Nikkiso Co., Ltd.).

(Initial viscosity)
2 using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., R100-type viscometer model RE100L).
The viscosity at 5°C was measured.
(Viscosity after storage for 1 week at 40℃)
After sealing the container tightly and storing it at 40°C for one week, the viscosity at 25°C was measured using the E-type viscometer described above. The viscosity change rate was determined by the formula (viscosity after 1 week at 40°C/initial viscosity)×100.

According to Examples A1 to A4, the change in viscosity after storage at 40° C. for one week was small compared to the initial viscosity. On the other hand, Comparative Examples A2 to A5 showed large changes in viscosity and poor storage stability.

<Dye-dispersed resist composition for color filters>
The dye dispersion compositions for color filters of Examples A1 to A4 and Comparative Examples A1 to A5, alkali-soluble resin, photopolymerizable compound, photoinitiator, and solvent were stirred at high speed so that the compositions were as shown in Table 2 below. After uniformly mixing using a machine, the mixture was filtered through a membrane filter with a pore size of 3 μm to obtain dye-dispersed resist compositions for color filters of Examples B1 to B4 and Comparative Examples B1 to B5.

(Evaluation of color characteristics of dye-dispersed resist composition for color filter)
The dye-dispersed resist compositions for color filters of Examples B1 to B4 and Comparative Examples B1 to B5 were applied onto a glass substrate using a spin coater. Next, after pre-baking at 100°C for 3 minutes, exposure was performed using a high-pressure mercury lamp, and further post-baking was performed at 230°C for 30 minutes. Next, the contrast, brightness Y, and film thickness of each resist at chromaticity x=0.4200 were measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2500PC, C light source, 2° field of view).

According to Examples B1 to B4, which are examples in accordance with the present invention, it was possible to obtain a sufficiently high contrast and at the same time achieve the desired Y value after post-baking.
On the other hand, in all of Comparative Examples B1 to B5, at least one of the contrast and the Y value was low. Comparative Examples B1 and B2 had a low Y value, and Comparative Examples B3 to B5 had a particularly low contrast.
According to the above results, the present invention was able to provide a color filter with appropriate contrast, y, and Y values.

Claims (7)

Contains a micronized insoluble xanthene dye, a dispersant that is an acrylic block polymer, a dispersion aid that is a phenyl group-containing phosphoric acid, an alkali-soluble resin, and an organic solvent,
The finely divided insoluble xanthene dye is a dye dispersion composition for color filters, and has a particle size distribution of D50 of 0.040 to 0.050 μm. The dye dispersion composition for color filters according to claim 1, wherein the dispersant, which is an acrylic block polymer, has an amine value of 5 to 100 mgKOH/g. The dye dispersion composition for a color filter according to claim 1 or 2, wherein the micronized insoluble xanthene dye has a structure shown in the following chemical formula 1 and/or the following chemical formula 2 .
[In the structural formula of Chemical Formula 1, R ¹ to R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent saturated hydrocarbon group having a substituent. represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be saturated, and -CH ₂ - contained in the saturated hydrocarbon group is replaced with -O-, -CO- or -NR ¹¹ -. You can leave it there. R ¹ and R ² may be bonded to each other and combined with a nitrogen atom to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be bonded to each other and combined with a nitrogen atom to form a nitrogen atom-containing ring. You may form a ring containing
R ⁵ is -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ is represented.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ^5s may be the same or different.
X represents a halogen atom.
Z ⁺ represents N(R ¹¹ ) ₄ ⁺ , Na ⁺ or K ⁺ , and the four R ^11s may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and are included in the saturated aliphatic hydrocarbon group - CH ₂ - may be replaced with -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ are bonded to each other and together with the nitrogen atom, form a 3- to 10-membered It may form a nitrogen-containing heterocycle.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]
[In the structural formula of Chemical Formula 2, R ¹ to R ⁴ and R ⁶ and R ⁷ are the same as the groups in Chemical Formula 1 above. ] The dye dispersion composition for color filters according to claim 2 or 3 , wherein the amine contained in the dispersant which is an acrylic block polymer is a tertiary amine or a quaternary amine. The dye dispersion composition for a color filter according to any one of claims 1 to 4 , wherein the amine moiety is localized in the molecule of the block polymer of the dispersant, which is an acrylic block polymer. The dye dispersion composition for color filters according to any one of claims 1 to 5 , wherein the alkali-soluble resin has an acid value of 5 to 250 mgKOH/g. A dye-dispersed resist composition for color filters, comprising the dye-dispersed composition for color filters according to any one of claims 1 to 6 .