JP5668539B2 - Coloring composition for color filter, color filter, and color liquid crystal display element - Google Patents

Description

  The present invention relates to a coloring composition for a color filter, a color filter, and a color liquid crystal display element. More specifically, the present invention is used for a transmissive or reflective color liquid crystal display element, solid-state imaging element, organic EL display element, electronic paper, and the like. The present invention relates to a colored composition used for forming a colored layer useful for a color filter, a color filter including a colored layer formed using the colored composition, and a color liquid crystal display element including the color filter.

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. There is known a method (Patent Documents 1 and 2) for obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known. Furthermore, a method of obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (Patent Document 4).

  By the way, in the field of color filters used for liquid crystal display elements and solid-state image sensors, pigments used tend to be increasingly atomized with the demand for higher brightness and higher contrast. In order to realize such a stable and good dispersibility of the atomized pigment, it is known that a dispersant is effective. Various methods (Patent Documents 5 to 6) for improving the dispersibility of pigments using such a dispersant and improving not only contrast and dispersion stability but also developability have been proposed.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2003-26949 A JP 2009-25813 A

However, even with the methods described in Patent Documents 5 to 6, it is difficult to realize the recent demands for high contrast, high color purity, and high brightness of color liquid crystal display elements, and mass production of color filters is also possible. It is hard to say that various problems such as developability can be solved. For this reason, there is a strong demand for the development of a coloring composition for a color filter that realizes the recent demands for high contrast, high color purity, and high brightness, and is excellent in developability and the like.
Therefore, the subject of this invention is providing the coloring composition for color filters which is excellent in chromaticity characteristic, and with favorable developability and storage stability. Furthermore, the subject of this invention is providing the color liquid crystal display element which comprises the color filter provided with the colored layer formed from the said coloring composition, and the said color filter.

  In view of this situation, the present inventors have conducted intensive research and found that the above problems can be solved by using a block copolymer having a specific repeating unit, and have completed the present invention.

That is, the present invention comprises the following components (A), (B) and (C);
(A) a colorant containing a pigment,
(B) A block copolymer having a repeating unit (1) represented by the following formula (1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group. A block copolymer having an A block containing the repeating unit (1) and a B block containing the repeating unit (2) and the repeating unit (3),
(C) The coloring composition for color filters characterized by containing a crosslinking agent is provided.

In [Equation (1), R ¹ represents a hydrogen atom or a methyl group, Z is ^{-N + R 2 R 3 R 4} Y - ( where, R ² to R ⁴ are independently of each other, hydrogen atom, or Represents a hydrocarbon group which may have a substituent, and Y ⁻ represents a counter anion.), —NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom or a substituent; Represents a hydrocarbon group which may have a group), or a nitrogen-containing heterocyclic group which may have a substituent, and X ¹ represents a divalent linking group. ]

In [Equation (2), R ⁷ independently of one another, an alkylene group having 2 to 4 carbon atoms, R ⁸ represents an alkyl group having 1 to 6 carbon atoms, R ⁹ represents a hydrogen atom or a methyl group , N represents an integer of 1 to 150. ]

  Moreover, this invention provides the color liquid crystal display element which comprises the color filter provided with the colored layer formed using the said coloring composition, and this color filter. Furthermore, the present invention provides a colorant dispersion for a color filter comprising the colorant containing the pigment (A), the block copolymer (B) and the solvent (F). . Here, the “colored layer” means each color pixel, black matrix, black spacer, etc. used in the color filter.

If the coloring composition of this invention is used, the color filter which has each color pixel which is excellent in chromaticity characteristic can be obtained. Moreover, the coloring composition for color filters of this invention is excellent also in developability and storage stability.
Therefore, the coloring composition for color filters of the present invention includes color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used very suitably for the production of various color filters.

Hereinafter, the present invention will be described in detail.
Color Filter Color Composition Hereinafter, the components of the color filter color composition of the present invention (hereinafter simply referred to as “color composition”) will be described.

-(A) Colorant-
The coloring composition of the present invention contains a pigment as the colorant (A). The pigment is not particularly limited, and may be an organic pigment or an inorganic pigment. In this invention, a pigment can be used individually or in mixture of 2 or more types. Of course, a mixture of an organic pigment and an inorganic pigment can also be used.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists). Specific examples include those with the following color index (CI) names.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;

C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  Examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide green. , Cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.

  In the present invention, the pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment is preferably used by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  By the way, in a coloring composition for a color filter, by using a dye as a colorant, it is possible to achieve high brightness and high contrast that cannot be achieved by a pigment alone. However, when a dye is used as a colorant in the conventional coloring composition, alkali developability is significantly deteriorated (see Comparative Example 4). On the other hand, in the colored composition of the present invention, by using the block copolymer (B) as a pigment dispersant, even when a pigment and a dye are used in combination as a colorant, alkali developability A good colored composition can be obtained (see Example 14).

  Examples of the dye include compounds having the following color index (CI) names.

C. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Azo dyes such as Moldant Black 7;
C. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Anthraquinone dyes such as Disperse Blue 60;
C. I. Phthalocyanine dyes such as Pad Blue 5;
C. I. Basic Blue 3, C.I. I. Quinone imine dyes such as Basic Blue 9;
C. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Quinoline dyes such as Disperse Yellow 64;
C. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Nitro dyes such as Disperse Yellow 42;
Methine dyes such as Disperse Yellow 201.

  When using dye as a coloring agent in this invention, dye can be used individually or in mixture of 2 or more types.

  (A) The content ratio of the colorant is usually 5 to 70% by mass in the solid content of the coloring composition, preferably from the point of forming a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties. 5 to 60% by mass. Here, solid content is components other than the solvent mentioned later.

-(B) Block copolymer-
The block copolymer (B) in the present invention has the repeating unit (1), the repeating unit (2) and the repeating unit (3), and the A block having the repeating unit (1) and the repeating unit (2). And having a B block having the repeating unit (3), it functions as a dispersant for the colorant (A).

The repeating unit (1) is represented by the above formula (1).
In the above formula (1), R ¹ is preferably a methyl group among a hydrogen atom and a methyl group.
Z represents —N ⁺ R ² R ³ R ⁴ Y ⁻ , —NR ⁵ R ⁶ or a nitrogen-containing heterocyclic group which may have a substituent, and R ^{2 to} R ⁶ are independently of each other. , A hydrogen atom, or a hydrocarbon group that may have a substituent, the term “hydrocarbon group” in the present invention means an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. It may be any of linear, branched and cyclic forms, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and the unsaturated bond may be in the molecule or at the end. You may have.
As said aliphatic hydrocarbon group, a C1-C20 (preferably 1-12) aliphatic hydrocarbon group is preferable, More specifically, a C1-C20 (preferably 1-12) alkyl is preferable. Group, an alkenyl group having 2 to 20 (preferably 2 to 12) carbon atoms, and an alkynyl group having 2 to 20 (preferably 2 to 12) carbon atoms. Moreover, as said alicyclic hydrocarbon, a C3-C20 (preferably 3-12) alicyclic hydrocarbon group is preferable, More specifically, it is C3-C20 (preferably 3-12). ) Cycloalkyl group. Further, the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms), more specifically 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms). And an aralkyl group having 7 to 16 (preferably 7 to 12) carbon atoms. Here, in the present invention, the “aryl group” refers to a monocyclic to tricyclic aromatic hydrocarbon group.
In addition, examples of the substituent in R ^{2 to} R ⁶ include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a carboxyl group, and an alkoxy group. be able to.
Among them, as the hydrocarbon group in R ² to R ^6, the alkyl group having 1 to 12 carbon atoms (preferably 1 to 6), an aralkyl group 7-16 carbon atoms (preferably 7 to 12) preferably a methyl group , Ethyl group, propyl group, butyl group and benzyl group are particularly preferable.

In the present invention, the “nitrogen-containing heterocyclic group” refers to a heterocyclic group having at least one nitrogen atom as a ring component, and a heterocyclic monocyclic group or a condensed heterocyclic group formed by condensing two of these. A cyclic group is preferred. These heterocyclic groups may be an unsaturated ring or a saturated ring, and may have a hetero atom (for example, an oxygen atom or a sulfur atom) other than a nitrogen atom in the ring.
Examples of the unsaturated heterocyclic ring include a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a triazole ring, an imidazoline ring, and a tetrahydropyrimidine ring. Examples of the saturated heterocyclic ring include a morpholine ring, piperidine ring, piperazine ring and the like. Examples of the substituent in the nitrogen-containing heterocyclic group include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a carboxyl group, an ester group, an ether group, a hydroxyl group, an amino group, an amide group, a thiol group, and a thioether group. Is mentioned.

  The heteromonocyclic group is preferably a 5- to 7-membered ring, and specific examples include groups having a basic skeleton represented by the following formula (1-1) or (1-2). The group may further have a substituent.

In formula (1-1), R represents a hydrogen atom or a hydrocarbon group which may have a substituent, and “*” represents a bond. The same thing as R < ² > is mentioned.

  In the formula (1-2), “*” indicates a bond.

  Specific examples of the condensed heterocyclic group include groups having a basic skeleton represented by the following formulas (1-3) to (1-5). These heterocyclic monocyclic groups have a substituent. You may do it.

  In formulas (1-3) to (1-5), “*” indicates a bond.

In the above formula (1), examples of the divalent linking group (X ¹ ) include a methylene group, an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6), an arylene group, and a —CONH—R ¹¹ — group. , —COO—R ¹² — group and the like. Here, R ¹¹ and R ¹² are each independently a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6), or an ether group having 2 to 10 carbon atoms (alkyleneoxyalkylene). Group). Among these, X ¹ is preferably a —COO—R ¹² — group, and R ¹² is preferably an alkylene group having 2 to 6 carbon atoms.

In the above formula (1), examples of Y ⁻ include halogen ions such as Cl ⁻ , Br ⁻ and I ⁻ , and counter anions of acids such as ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ and PF ₆ ^−. .

The repeating unit (2) is represented by the above formula (2).
In the above formula (2), R ⁷ represents an alkylene group having 2 to 4 carbon atoms, but may be composed of two or more alkylene groups, and is preferably an ethylene group and / or a propylene group.
R ⁸ represents an alkyl group having 1 to 6 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, or a butyl group.
R ⁹ is preferably a methyl group among a hydrogen atom and a methyl group.
Although n shows the integer of 1-150, the integer of 1-20 is preferable, the integer of 1-10 is more preferable, and the integer of 1-5 is especially preferable.

The repeating unit (3) has an acidic group, but the acidic group is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfo group, —SO ₂ NH ₂ , and —C (CF ₃ ) _2. -OH etc. are mentioned. In the present invention, the acidic group is preferably a phenolic hydroxyl group or a carboxyl group, and particularly preferably a carboxyl group, from the viewpoint of dispersibility and alkali developability of the resulting colored composition.

  Examples of the repeating unit (3) include a repeating unit represented by the following formula (3).

In Formula (3), R ¹⁰ represents a hydrogen atom or a methyl group, A represents an acidic group, and X ² represents a single bond or a divalent linking group.

In the above formula (3), R ¹⁰ is preferably a methyl group among a hydrogen atom and a methyl group.
Examples of the divalent linking group (X ² ) include a methylene group, an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6), an arylene group, a —CONH—R ¹¹ — group, and —COO—R ¹² —. Group, —OCOR ¹³ — group, —R ¹⁴ —OCO—R ¹⁵ —, —COO— (C _m H _2m COO) ₁ —C _m H _2m — group, —COO—R ¹⁶ —OCO—R ¹⁷ — and the like. Can be mentioned. Here, R ^{11 to} R ¹⁵ are each independently a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6), or an ether group having 2 to 10 carbon atoms (alkyleneoxyalkylene). Group, m represents an integer of 1 to 10, l represents an integer of 1 to 4, R ¹⁶ represents a methylene group or an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6 carbon atoms), R ¹⁷ is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6), a cyclohexane-1,2-diyl group or a phenylene group (for example, 1,2-phenylene group, 1,4-phenylene). Group).
Among them, X ² may be a single bond, a phenylene group, a —COO—R ¹² — group, a —COO— (C _m H _2m COO) ₁ —C _m H _2m — group or a —COO—R ¹⁶ —OCO—R ^17. -Is preferred.

  (B) The block copolymer may have a repeating unit other than the above (hereinafter referred to as “repeating unit (4)”). Examples of such a repeating unit (4) include styrene monomers such as styrene and α-methylstyrene; (meth) acrylamide; vinyl acetate; repeating units derived from monomers such as acrylonitrile, the following formula ( The repeating unit represented by 4) is mentioned. Among these, the repeating unit (4) preferably has a repeating unit represented by the following formula (4) from the viewpoint of dispersibility. Here, in the present invention, “(meth) acrylate” means “acrylate or methacrylate”.

In Formula (4), R ¹⁸ represents a hydrogen atom or a hydrocarbon group which may have a substituent, and R ¹⁹ represents a hydrogen atom or a methyl group.

In the above formula (4), R ¹⁹ is preferably a methyl group among a hydrogen atom and a methyl group.
As the hydrocarbon group for R ¹⁸ include those the same as above R ^2, it may have the same substituents as the R ^2. Among them, as R ¹⁸ , an alkyl group having 1 to 12 carbon atoms (preferably 1 to 10), an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 16 carbon atoms are preferable, and a methyl group, an ethyl group, and propyl group are preferable. Group, butyl group, 2-ethylhexyl group, phenyl group, benzyl group and phenylethyl group are particularly preferred.

  The molecular weight of the (B) block copolymer is a polymethyl methacrylate equivalent weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: DMF), preferably 1 5,000 to 30,000, particularly preferably 5,000 to 15,000. The ratio (Mw / Mn) of (B) the block copolymer Mw and the number average molecular weight in terms of polymethyl methacrylate (hereinafter referred to as “Mn”) measured by GPC (elution solvent: DMF) is: Preferably it is 1.0-1.8, More preferably, it is 1.0-1.7, More preferably, it is 1.0-1.6, Most preferably, it is 1.0-1.3. (B) By making a block copolymer into such an aspect, the coloring composition excellent in the dispersibility and alkali developability can be obtained.

(B) The block copolymer is not particularly limited as long as it has the repeating unit (1) as the A block and the repeating unit (2) and the repeating unit (3) as the B block, respectively. A polymer or an ABA block copolymer may be used.
(B) The copolymerization ratio (mass ratio) of A block / B block in the block copolymer is preferably 1/99 to 90/10, more preferably 10/90 to 70/30, and 15/85 to 60 /. 30 is particularly preferred.

  In the A block, the repeating unit (1) may be contained in two or more kinds in one A block. In that case, each repeating unit is randomly copolymerized or block copolymerized in the A block. It may be contained in any aspect.

The B block has, for example, the repeating unit (2) and the repeating unit (3), or the repeating unit (2), the repeating unit (3), and the repeating unit (4). From the viewpoint of dispersibility, the B block preferably has a repeating unit (2), a repeating unit (3), and a repeating unit (4).
The repeating unit constituting the B block may be contained in any of random copolymerization and block copolymerization. In addition, each repeating unit may be contained in two or more types in one B block. In that case, each repeating unit is in any form of random copolymerization and block copolymerization in the B block. It may be contained.

  (B) In the block copolymer, the copolymerization ratio of the repeating unit (1) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 15 to 40% by mass in all the repeating units. It is. The copolymerization ratio of the repeating unit (2) is preferably 1 to 50% by mass, more preferably 2 to 40% by mass in all repeating units. The copolymerization ratio of the repeating unit (3) is preferably 0.5 to 20% by mass, more preferably 0.5 to 15% by mass, and further preferably 1 to 11% by mass in all the repeating units. The copolymerization ratio of the repeating unit (4) is preferably 10 to 80% by mass, more preferably 20 to 70% by mass in all the repeating units. By copolymerizing each repeating unit at such a ratio, a colored composition having excellent dispersibility and alkali developability can be obtained.

  Such a (B) block copolymer can be produced by, for example, living polymerizing a monomer that gives each of the above repeating units. Examples of the living polymerization method include JP-A-9-62002; JP-A-2002-31713; Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984); C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981); Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985); Hatada, K .; Ute, et al, Polym. J. et al. 18, 1037 (1986); Koichi Right-hand, Koichi Hatada, Polymer Processing, 36, 366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Thesis, 46, 189 (1989); Kuroki, T .; Aida, J .; Am. Chem. Soc, 109, 4737 (1987); Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985); Y. Sogoh, W .; R. Hertler et al, Macromolecules, 20, 1473 (1987); Polym. Sci. Part A Polym. Chem. 47, 3773-3794 (2009); Polym. Sci. Part A Polym. Chem. 47, 3544-3557 (2009), etc., can be used.

Examples of the monomer that gives the repeating unit (1) and in which Z in the formula (1) is —N ⁺ R ² R ³ R ⁴ Y ^— or —NR ⁵ R ⁶ include (meta ) Acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) acryloyloxyethyl Benzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropylene Examples include ru (meth) acrylate and diethylaminopropyl (meth) acrylate. The repeating unit (1) in which Z is —N ⁺ R ² R ³ R ⁴ Y ^— is, for example, a monomer (for example, dimethylaminoethyl (meth) acrylate) in which Z is —NR ⁵ R ^6. After the polymerization, the polymer can be obtained by reacting a halogenated hydrocarbon compound such as benzyl chloride to partially quaternize the amino group.

  Examples of the monomer that gives the repeating unit (1) and in which Z in the formula (1) is a nitrogen-containing heterocyclic group include, for example, a compound group α (monomer 1 to 18) represented by the following formula: And a compound represented by the following formula (5). In addition, the monomer which gives repeating unit (1) can be used individually or in mixture of 2 or more types.

  Examples of the monomer that gives the repeating unit (2) include 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol ( And (meth) acrylate and methoxydipropylene glycol (meth) acrylate. These can be used alone or in admixture of two or more.

  Examples of the monomer that gives the repeating unit (3) include (meth) acrylic acid, maleic acid, maleic anhydride, (meth) acrylic acid carboxymethyl ester, (meth) acrylic acid 2-carboxy-ethyl ester, and amber. Acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylbenzoic acid, p-hydroxystyrene, p-hydroxy-α-methylstyrene, 2-acryloyloxy Ethylsulfonic acid, 2-methacryloxyethylsulfonic acid, sodium 2-acryloyloxyethylsulfonate, lithium 2-acryloyloxyethylsulfonate, ammonium 2-acryloyloxyethylsulfonate, 2-acryloyloxyethylsulfonic acid Imidazolium, 2-acryloiro Pyridinium xylethylsulfonate, sodium 2-methacryloxyethylsulfonate, lithium 2-methacryloxyethylsulfonate, ammonium 2-methacryloxyethylsulfonate, imidazolium 2-methacryloxyethylsulfonate, 2-methacryloxyethylsulfonic acid Examples include pyridinium, styrene sulfonic acid, sodium styrene sulfonate, lithium styrene sulfonate, ammonium styrene sulfonate, imidazolium styrene sulfonate, and pyridinium styrene sulfonate. These can be used alone or in admixture of two or more.

  Examples of the monomer that gives the repeating unit (4) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl. (Meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, and the like. These can be used alone or in admixture of two or more.

  (B) A block copolymer can be used individually or in mixture of 2 or more types. (B) Content of a block copolymer is 1-100 mass parts normally with respect to 100 mass parts of pigments, Preferably it is 5-70 mass parts, More preferably, it is 10-50 mass parts. (B) When there is too much content of a block copolymer, there exists a possibility that developability may be impaired.

In the present invention, a known dispersing agent may be further contained in order to improve dispersibility. Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Examples thereof include a dispersant, a fatty acid-modified polyester dispersant, an acrylic dispersant, and a pigment derivative.
Specific examples of such a dispersant include trade names of EFKA (manufactured by EFKA Chemicals BV (EFKA)), Disperbyk (manufactured by BYK (BYK)), Disparon (manufactured by Enomoto Kasei Co., Ltd.), Solsperse ( Lubrizol Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), F-Top (Tochem Products Co., Ltd.), MegaFuck (Dainippon Ink Chemical Co., Ltd.) , Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), and the like. Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivative of quinophthalone.

-(C) Crosslinking agent-
In the present invention, (C) a crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, (C) the crosslinking agent is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a caprolactone-modified polyfunctional ( (Meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, hydroxyl-functional (meth) acrylate and polyfunctional isocyanate obtained by reacting with polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid The polyfunctional (meth) acrylate which has a carboxyl group obtained by making an anhydride react can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide modified tri (meth) acrylate, tri Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol Dipentaerythritol ethylene oxide and / or propylene oxide modified penta (meth) acrylate, di It can be mentioned pointer ethylene oxide erythritol and / or propylene oxide-modified hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N, N, N, N-hexa (alkoxymethyl) melamine, N, N, N, N-tetra (alkoxymethyl). ) Benzoguanamine, N, N, N, N-tetra (alkoxymethyl) glycoluril and the like.

Of these polyfunctional monomers, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, Polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N, N, N, N-hexa (alkoxymethyl) melamine, N, N, N, N-tetra (alkoxymethyl) ) Benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In the present invention, the crosslinking agent (C) can be used alone or in admixture of two or more.

  In the present invention, the content of the (C) crosslinking agent is preferably 10 to 1,000 parts by mass, and particularly preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. In this case, if the content of the polyfunctional monomer is too small, sufficient curability may not be obtained. On the other hand, if the content of the polyfunctional monomer is too large, when the color composition of the present invention is imparted with alkali developability, the alkali developability is lowered, and on the unexposed portion of the substrate or the light shielding layer. There is a tendency that dirt, film residue, etc. are likely to occur.

-(D) Binder resin-
The coloring composition of the present invention can contain (D) a binder resin. Thereby, alkali developability and the binding property to a board | substrate can be improved to a coloring composition. Such a binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). (D1) ”) and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as“ unsaturated monomer (d2) ”).

Examples of the unsaturated monomer (d1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (d1) can be used alone or in admixture of two or more.

Examples of the unsaturated monomer (d2) include:
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; aromatics such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene Vinyl compounds;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (n = 2 -10) methyl ether (meth) acrylate, polypropylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) ) Mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, Glyce Mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meta ) (Meth) acrylic acid esters such as acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (d2) can be used alone or in admixture of two or more.

  In the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2), the copolymerization ratio of the unsaturated monomer (d1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (d1) within such a range, a colored composition having excellent alkali developability and storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. Copolymers disclosed in JP-A-10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like. Can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

  The binder resin in the present invention has a polystyrene-reduced weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, preferably 3,000 to 50,000. If the weight average molecular weight is too small, the residual film ratio of the resulting coating may decrease, the pattern shape, heat resistance, etc. may be impaired, and the electrical characteristics may deteriorate, while if too large, the resolution will decrease. Or the shape of the pattern may be damaged, and dry foreign matter may be easily generated during application by the slit nozzle method.

  In addition, the ratio (weight average molecular weight / number average molecular weight) of the weight average molecular weight of the binder resin in the present invention and the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) is preferably 1.0 to 5. 0.0, more preferably 1.0 to 3.0.

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, weight average molecular weight, weight average molecular weight / number average molecular weight can also be controlled by the method.

  In this invention, binder resin can be used individually or in mixture of 2 or more types.

  In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.

-(E) Photopolymerization initiator-
The coloring composition of the present invention can contain (E) a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The (E) photopolymerization initiator used in the present invention generates an active species capable of initiating the polymerization of the above (C) crosslinking agent upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound.

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

  Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′. -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-(F) Solvent-
The coloring composition of the present invention usually comprises (A) a colorant containing a pigment in (F) a solvent, (B) a block copolymer and, if necessary, another dispersant and (D) part of a binder resin. In addition, for example, a bead mill, a roll mill or the like is mixed and dispersed while being pulverized to obtain a pigment dispersion. Next, (C) a crosslinking agent and (D) a binder resin ( E) It is prepared by a method in which a photopolymerization initiator and an additional (F) solvent are added and mixed. (F) As a solvent, as long as components (A) to (C) and other components constituting the colored composition are dispersed or dissolved and do not react with these components and have appropriate volatility. Can be appropriately selected and used. However, when preparing the pigment dispersion, from the viewpoint of dispersibility and stability, (f1) a solvent having a hydroxyl group (hereinafter also referred to as “solvent (f1)”) and (f2) having a hydroxyl group. It is preferable to use a solvent that does not (hereinafter also referred to as “solvent (f2)”).

Among such solvents, as the solvent (f1), for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Examples thereof include keto alcohols such as diacetone alcohol.

  Of these solvents (f1), (poly) alkylene glycol monoalkyl ethers are preferable, and propylene glycol monomethyl ether and propylene glycol monoethyl ether are particularly preferable. A solvent (f1) can be used individually or in mixture of 2 or more types.

Moreover, as a solvent (f2), for example,
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  Of these solvents (f2), (poly) alkylene glycol monoalkyl ether acetates, ethers, ketones, diacetates, and alkoxycarboxylic acid esters are preferred, particularly ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. , Propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl are preferred. A solvent (f2) can be used individually or in mixture of 2 or more types.

  In the present invention, the content ratio (f1 / f2) of the solvent (f1) to the solvent (f2) in the colorant dispersion is preferably 0.5 / 99.5 to 40/60, more preferably 1/99 to 30/70, particularly preferably 5/95 to 25/75.

  Although the content of the solvent is not particularly limited, the total concentration of each component excluding the pigment dispersion or the solvent of the colored composition is the same regardless of whether it is a pigment dispersion or a colored composition. The amount of 5 to 50% by mass is preferable, and the amount of 10 to 40% by mass is particularly preferable. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable coating property and stability can be obtained.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio Residue improving agents such as succinic acid; development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. And the like, and the like.

Color filter and method for producing the same The color filter of the present invention includes a colored layer formed using the colored composition of the present invention.

  As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a liquid composition of a radiation-sensitive composition in which a red colorant is dispersed on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

  Next, each colored radiation-sensitive composition of green or blue is used, and each colored radiation-sensitive composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, so that the green pixel array and blue Are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. Using the radiation-sensitive composition, it can be formed in the same manner as in the case of forming the pixel.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When the colored radiation-sensitive composition is applied to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method may be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

  The coating thickness is usually 0.6 to 8.0 μm, preferably 1.2 to 5.0 μm, as the film thickness after drying.

  Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples of the light source include a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. Radiation having a wavelength in the range of 190 to 450 nm is preferable.

Exposure of the radiation is generally preferred 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a liquid composition of a colored composition in which a red colorant is dispersed in the formed partition wall is discharged by an ink jet apparatus, and then prebaked to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.

  Subsequently, using each coloring composition of green or blue, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. Thus, the film thickness of the pixel formed by the ink jet method is approximately the same as the thickness of the black matrix.

A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.
Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful for color liquid crystal surface elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
The color liquid crystal display element of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

  The color liquid crystal display element of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light using a red LED, a green LED, and a blue LED having independent spectra, a white LED that obtains white light by mixing colors by combining the red LED, the green LED, and the blue LED, White LED that obtains white light by color mixing by combining blue LED, red LED and green phosphor, White LED that obtains white light by color mixing by combining blue LED, red light emitting phosphor and green light emitting phosphor, Blue LED and YAG system White LED that obtains white light by mixing phosphors, white LED that obtains white light by mixing blue LED, orange light emitting phosphor and green light emitting phosphor, UV LED, red light emitting phosphor, green light emitting phosphor and blue A white LED that obtains white light by mixing colors by combining light emitting phosphors can be exemplified.

  The color liquid crystal display element of the present invention includes a TN (twisted nematic) type, a STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical aligned type) type, and an OCB (optically conjugated type). An appropriate liquid crystal mode can be applied.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. In addition, Example 7 shown below is a reference example.

<(B) Synthesis of block copolymer>
Synthesis example 1
In a flask equipped with a stirrer, 1.4 g of methacrylic acid (hereinafter referred to as “MA”), methoxypolyethylene glycol monomethacrylate (PME-200 manufactured by NOF Corporation) (hereinafter referred to as “PME-200”). 5.6 g, normal butyl methacrylate (hereinafter referred to as “nBMA”) 5.0 g, 2-ethylhexyl methacrylate (hereinafter referred to as “EHMA”) 5.0 g, benzyl methacrylate (hereinafter referred to as “BzMA”). 1.7 g, methyl methacrylate (hereinafter referred to as “MMA”) 7.8 g, 2,2′-azobisisobutyronitrile (hereinafter referred to as “AIBN”) 303 mg, and pyrazole-1 -Dissolve 781 mg of dithiocarboxylic acid cyano (dimethyl) methyl ester in 30 mL of toluene, 30 minutes The bubbling element was carried out. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution in which 73 mg of AIBN and 1.4 g of dimethylaminoethyl methacrylate (hereinafter referred to as “DAMA”) were dissolved in 20 mL of toluene and purged with nitrogen for 30 minutes was added to the above reaction solution, and the living radical at 60 ° C. for 24 hours. Polymerization was performed. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer solution which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, EHMA, BzMA, and MMA was obtained. The obtained block copolymer is referred to as “block copolymer (B-1)”.

Synthesis example 2
In a flask equipped with a stir bar, 1.4 g of MA, 8.4 g of PME-200, 12.9 g of nBMA, 224 mg of AIBN, and 579 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 mL of toluene, and 30 Nitrogen bubbling was performed for a minute. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 57 ° C., and this temperature was maintained for 34 hours to perform living radical polymerization.
Next, a solution obtained by dissolving 277 mg of AIBN and 5.3 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C. for 34 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, and nBMA was obtained. The obtained block copolymer is referred to as “block copolymer (B-2)”.

Synthesis example 3
In a flask equipped with a stir bar, 1.4 g of MA, 4.2 g of PME-200, 2.8 g of nBMA, 3.4 g of MMA, 139 mg of AIBN and 357 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added to 30 mL of toluene. Dissolved and bubbled with nitrogen for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution obtained by dissolving 277 mg of AIBN and 16.2 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, and MMA was obtained. The obtained block copolymer is referred to as “block copolymer (B-3)”.

Synthesis example 4
In a flask equipped with a stir bar, 1.4 g of MA, 2.8 g of PME-200, 2.8 g of nBMA, 2.8 g of BzMA, 101 mg of AIBN, and 261 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added to 30 mL of toluene. Dissolved and bubbled with nitrogen for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution prepared by dissolving 946 mg of AIBN and 18.2 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, and BzMA was obtained. The obtained block copolymer is referred to as “block copolymer (B-4)”.

Synthesis example 5
In a flask equipped with a stir bar, 0.5 g of MA, 10.6 g of PME-200, 10.9 g of nBMA, 199 mg of AIBN and 513 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 mL of toluene, Nitrogen bubbling was performed for a minute. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 57 ° C., and this temperature was maintained for 34 hours to perform living radical polymerization.
Next, a solution obtained by dissolving 306 mg of AIBN and 5.9 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C. for 34 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, and nBMA was obtained. The obtained block copolymer is referred to as “block copolymer (B-5)”.

Synthesis Example 6
In a flask equipped with a stir bar, 3.1 g of MA, 2.8 g of PME-200, 3.6 g of nBMA, 3.6 g of EHMA, 1.4 g of BzMA, 7.6 g of MMA, 312 mg of AIBN and cyano (dimethyl) pyrazole-1-dithiocarboxylate 768 mg of methyl ester was dissolved in 30 mL of toluene, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 57 ° C., and this temperature was maintained for 34 hours to perform living radical polymerization.
Next, a solution obtained by dissolving 336 mg of AIBN and 5.9 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C. for 34 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, EHMA, BzMA, and MMA was obtained. Let the obtained block copolymer be "block copolymer (B-6)."

Synthesis example 7
In a flask equipped with a stir bar, 5.6 g of MA, 4.8 g of PME-200, 11.8 g of nBMA, 270 mg of AIBN, and 696 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 mL of toluene, and 30 Nitrogen bubbling was performed for a minute. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution obtained by dissolving 306 mg of AIBN and 5.9 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, and nBMA was obtained. The obtained block copolymer is referred to as “block copolymer (B-7)”.

Synthesis Example 8
In a flask equipped with a stir bar, 11.2 g of MA, 2.8 g of PME-200, 2.8 g of nBMA, 1.4 g of EHMA, 1.4 g of BzMA, 2.8 g of MMA, 332 mg of AIBN and cyano (dimethyl) pyrazole-1-dithiocarboxylate 856 mg of methyl ester was dissolved in 30 mL of toluene, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution obtained by dissolving 291 mg of AIBN and 5.6 g of DAMA in 20 mL of toluene and replacing with nitrogen for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, EHMA, BzMA, and MMA was obtained. Let the obtained block copolymer be "block copolymer (B-8)."

Synthesis Example 9
In a flask equipped with a stir bar, MA 1.4 g, PME-200 1.9 g, nBMA 3.5 g, EHMA 3.5 g, BzMA 1.6 g, MMA 7.2 g, AIBN 337 mg and pyrazole-1-dithiocarboxylate cyano (dimethyl) 621 mg of methyl ester was dissolved in 30 mL of toluene, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 62 ° C., and this temperature was maintained for 20 hours to carry out living radical polymerization.
Next, a solution obtained by dissolving 640 mg of AIBN and 8.8 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 62 ° C. for 20 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, EHMA, BzMA, and MMA was obtained. The obtained block copolymer is referred to as “block copolymer (B-9)”.

Synthesis Example 10
In a flask equipped with a stir bar, MA 1.4 g, PME-200 7.3 g, nBMA 5.6 g, EHMA 2.8 g, BzMA 1.5 g, MMA 1.5 g, AIBN 197 mg and pyrazole-1-dithiocarboxylate cyano (dimethyl) 507 mg of methyl ester was dissolved in 30 mL of toluene, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 57 ° C., and this temperature was maintained for 34 hours to perform living radical polymerization.
Next, 312 mg of AIBN and 7.8 g of the above monomer 1 were dissolved in 20 mL of toluene and a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C. for 34 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from the monomer 1, and B block which has a repeating unit derived from MA, PME-200, nBMA, EHMA, BzMA and MMA was obtained. The obtained block copolymer is referred to as “block copolymer (B-10)”.

Synthesis Example 11
To the flask, 594.35 g of tetrahydrofuran (hereinafter referred to as “THF”) and 10.98 g of lithium chloride (3.63% by mass concentration THF solution) were added and cooled to −60 ° C. Then, 7.89 g (15.36 mass% concentration hexane solution) of n-butyllithium was added and aged for 10 minutes.
Next, a mixed liquid of 4.04 g of 1-ethoxyethyl methacrylate (hereinafter referred to as “EEMA”), 61.33 g of nBMA, PME-200, and 26.19 g is dropped over 30 minutes, and the reaction is performed for 30 minutes after the dropwise addition. Continued. Gas chromatography (hereinafter referred to as “GC”) / GPC (mobile phase THF, DMF) was measured to confirm the disappearance of the monomer.
Next, 39.71 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after the addition. Then, GC · GPC (mobile phase DMF) was measured to confirm the disappearance of the monomer, and then the reaction was stopped by adding 3.21 g of methanol.
Deprotection of EEMA was performed by heating 200 g of a propylene glycol monomethyl ether acetate solution having a concentration of 50% by mass of the obtained precursor copolymer to 160 ° C. and reacting for 3 hours. Thereafter, propylene glycol monomethyl ether acetate was added to make the nonvolatile content 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, and nBMA was obtained. The obtained block copolymer is referred to as “block copolymer (B-11)”.

Synthesis Example 12
To the flask were added 578.66 g of THF and 11.20 g of lithium chloride (3.63% by mass concentration THF solution), and the mixture was cooled to −60 ° C. Then, 7.34 g of n-butyllithium (15.36 mass% concentration hexane solution) was added and aged for 10 minutes.
Subsequently, 4.30 g of MMA was added and the reaction was continued for 5 minutes. And after confirming disappearance of the monomer by GC measurement, when a part was sampled and GPC measurement was performed, a polymer having a molecular weight of 293 (2.92 mer) was formed.
Next, a mixed solution of EEMA 4.52 g, EHMA 19.80 g, nBMA 19.50 g, MMA 36.48 g, BzMA 15.03 g, PME-200, 11.99 g was added dropwise over 30 minutes, and the reaction was continued for 30 minutes after the addition. GC / GPC (mobile phase THF, DMF) was measured to confirm the disappearance of the monomer.
Next, 36.98 g of DAMA was dropped, and the reaction was continued for 30 minutes after the dropping. GC / GPC (mobile phase DMF) was measured to confirm the disappearance of the monomer, and then the reaction was stopped by adding 3.21 g of methanol.
Deprotection of EEMA was performed by heating 200 g of a propylene glycol monomethyl ether acetate solution having a concentration of 50% by mass of the obtained precursor copolymer to 160 ° C. and reacting for 3 hours. Thereafter, propylene glycol monomethyl ether acetate was added to make the nonvolatile content 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MA, PME-200, nBMA, EHMA, BzMA, and MMA was obtained. The obtained block copolymer is referred to as “block copolymer (B-12)”.

Comparative Synthesis Example 1
558.67 g of THF and 10.28 g of lithium chloride (3.63 mass% concentration THF solution) were added to the flask and cooled to −60 ° C. Thereafter, 7.60 g of n-butyllithium (15.36% by mass concentration hexane solution) was added and aged for 10 minutes.
Subsequently, 4.38 g of MMA was added and the reaction was continued for 5 minutes. And after confirming disappearance of the monomer by GC measurement, when a part was sampled and GPC measurement was performed, a polymer having a molecular weight of 346 (3.46 mer) was formed.
Next, a mixed solution of EHMA 17.08 g, nBMA 16.95 g, MMA 31.66 g, BzMA 8.01 g, PME-200, and 9.48 g was added dropwise over 30 minutes, and the reaction was continued for 30 minutes after the addition. GC / GPC (mobile phase THF, DMF) was measured to confirm the disappearance of the monomer.
Next, 42.98 g of DAMA was added dropwise, and the reaction was continued for 30 minutes after the addition. GC / GPC (mobile phase DMF) was measured to confirm the disappearance of the monomer, and then 2.40 g of methanol was added to stop the reaction. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, nBMA, EHMA, BzMA, and MMA was obtained. The obtained block copolymer is referred to as “block copolymer (b-1)”.

Comparative Synthesis Example 2
In a flask equipped with a stirrer, 1.4 g of MA, 8.4 g of PME-200, 12.9 g of nBMA, 5.3 g of DAMA, 451 mg of AIBN and 579 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added to 50 mL of toluene. Dissolved and bubbled with nitrogen for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 57 ° C., and this temperature was maintained for 34 hours to carry out radical polymerization.
Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. In this way, a random copolymer having repeating units derived from MA, PME-200, nBMA and DAMA was obtained. Let the obtained random copolymer be "copolymer (b-2)."

<Measurement of Mw and Mw / Mn>
Mw and Mn of the (B) block copolymer obtained in each of the above synthesis examples were measured by GPC having the following specifications. In Table 1, a measurement result is shown with the copolymerization ratio (mass%) of each monomer in (B) block copolymer.
Apparatus: GPC-104 (made by Showa Denko KK).
Column: KD-G, KF-603, KF-602, KF-601 were used in combination.
Mobile phase: DMF.

<Measurement of acid value>
The acid value of the (B) block copolymer obtained in each of the above synthesis examples was measured as follows. Table 1 shows the measurement results.
0.5 g of the block copolymer solution was precisely weighed to a unit of 1 mg and separated into a glass container. After diluting to 50 mL with propylene glycol monomethyl ether acetate, phenolphthalein was added, titrated with 0.1 N ethanolic potassium hydroxide aqueous solution, and the point colored in pink was the end point. Similarly, a blank test was performed. (B) The acid value (unit: mgKOH / g) was calculated from the dropwise addition amount of the block copolymer and 0.1N ethanolic potassium hydroxide aqueous solution in the blank test. In addition, the acid value in this invention represents the mg number of KOH required in order to neutralize 1 g of non volatile matters except the solvent of the block copolymer solution.

<Measurement of amine value>
The amine value of the (B) block copolymer obtained in each of the above synthesis examples was measured as follows. Table 1 shows the measurement results.
0.5 g of the block copolymer solution was precisely weighed to a unit of 1 mg and separated into a glass container. Acetic anhydride / acetic acid = 9/1 (volume ratio) 20 ml was added and dissolved, and left at room temperature for 3 hours. Thereafter, 30 mL of acetic acid was further added, and titration was performed with a 0.1 mol / L perchloric acid / acetic acid solution using a potentiometer AT-510 (manufactured by Kyoto Electronics Co., Ltd.). Similarly, a blank test was performed. (B) The amine value (unit: mgKOH / g) was calculated from the amount of the block copolymer and the 0.1 mol / L perchloric acid / acetic acid solution dropped in the blank test. The amine value in the present invention represents the number of mg of KOH equivalent to the acid required to neutralize 1 g of the nonvolatile content excluding the solvent of the block copolymer solution.

<Preparation of colorant dispersion>
Preparation Example 1
As a coloring agent, C.I. I. Pigment Green 58 (DIC) 9 parts by mass and C.I. I. 6 parts by mass of Pigment Yellow 150, 12.5 parts by mass of the block copolymer (B-1) solution (nonvolatile component = 40% by mass), 64.5 parts by mass of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether 8 as a solvent Using the mass part, it processed with the bead mill and prepared the colorant dispersion liquid (A-1).

Preparation Examples 2-14 and Comparative Preparation Examples 1-5
In Preparation Example 1, the same procedure as in Preparation Example 1 except that the types and amounts of the colorant, the block copolymer (B) and the solvent are changed as shown in Table 2. (A-19)
Was prepared.

<Evaluation of colorant dispersion>
The viscosity of the obtained colorant dispersion was measured using an E-type viscometer (manufactured by Tokyo Keiki). The obtained colorant dispersion was filled in a light-shielding glass container and allowed to stand at 23 ° C. for 14 days in a sealed state, and then the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki). Then, the increase rate of the viscosity after storage for 14 days with respect to the viscosity immediately after the preparation is calculated. When the increase rate is less than 5%, “A”, when 5% or more and less than 10%, “B”, 10% or more The case was evaluated as “C”. The evaluation results are shown in Table 2.

  In Table 2, “G58” means C.I. I. Pigment Green 58, “Y150” is C.I. I. Pigment Yellow 150, “B15: 6” means C.I. I. Pigment Blue 15: 6, “V23” is C.I. I. Pigment Violet 23, “Y179” is an organic dye C.I. I. Solvent Yellow 179, “PGMEA” is propylene glycol monomethyl ether acetate, “PGME” is propylene glycol monomethyl ether, and “BYK6919” is a commercially available dispersant BYK-LPN6919 (manufactured by BYK Corporation) Means each. Note that BYK-LPN6919 is a copolymer having a repeating unit (1) and a repeating unit (2) but not having a repeating unit having an acidic group, acid value = 0, amine value = 120 mgKOH / g ( Non-volatile content), non-volatile content = 60 mass%.

<Synthesis of binder resin>
Synthesis Example 13
In a flask equipped with a condenser and a stirrer, 44.0 g of p-vinylbenzyl glycidyl ether, 40.0 g of N-phenylmaleimide, and 16.0 g of BzMA are dissolved in 300 g of propylene glycol monomethyl ether acetate, and 8.0 g of AIBN and α-methyl are added. 8.0 g of styrene dimer was charged and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling and polymerized for 5 hours.
Next, 17.0 g of MA, 0.5 g of p-methoxyphenol and 4.4 g of tetrabutylammonium bromide were added to this reaction solution, and reacted at 120 ° C. for 9 hours. Further, 18.5 g of succinic anhydride was added and reacted at 100 ° C. for 6 hours, then washed twice with the liquid temperature kept at 85 ° C., and concentrated under reduced pressure to obtain a binder resin (D-1). A solution containing 33% by mass of was obtained. This binder resin (D-1) has a polystyrene equivalent weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) = 7,800, a polystyrene equivalent weight average molecular weight and number average measured by GPC (elution solvent: tetrahydrofuran). Ratio to molecular weight = 2.8.

Synthesis Example 14
In a flask equipped with a condenser and a stirrer, BzMA 30.0 g, nBMA 20.0 g, hydroxyethyl methacrylate 15.0 g, styrene 20.0 g and MA 15.0 g were dissolved in propylene glycol monomethyl ether acetate 200 g, and AIBN 3.0 g and α -5.0 g of methylstyrene dimer was charged and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling and polymerized for 5 hours to obtain a solution containing 33% by mass of binder resin (D-2). This binder resin (D-2) has a polystyrene-equivalent weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) = 10,000 and a polystyrene-equivalent weight average molecular weight and number average measured by GPC (elution solvent: tetrahydrofuran). Ratio to molecular weight = 2.5.

Synthesis Example 15
In a flask equipped with a condenser and a stirrer, 25.0 g of 3-methacryloyloxymethyl-3-ethyloxetane, 18.0 g of methacrylic acid, 9.0 g of mono-2-acryloxyethyl succinate, 10.0 g of N-phenylmaleimide, 24.0 g of BzMA and 14.0 g of hydroxyethyl methacrylate were dissolved in 300 g of propylene glycol monomethyl ether acetate, and 6.0 g of AIBN and 6.0 g of α-methylstyrene dimer were added, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling, and polymerized for 5 hours to obtain a precursor copolymer solution.
To 200 g of the obtained precursor copolymer solution, 13.4 g of 2-methacryloyloxyethyl isocyanate and 0.2 g of 4-methoxyphenol as a polymerization inhibitor were added and reacted at 90 ° C. for 2 hours. The reaction solution was washed twice with 75 g of ion exchange water per time and concentrated under reduced pressure to obtain a solution containing 33% by mass of the binder resin (D-3). Binder resin (D-3) is polystyrene equivalent weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) = 11,000, polystyrene equivalent weight average molecular weight and number average molecular weight measured by GPC (elution solvent: tetrahydrofuran). And the ratio was 1.9.

<Preparation and evaluation of coloring composition>
Preparation of coloring composition Example 1
100 parts by weight of the colorant dispersion (A-1), 33.5 parts by weight of the binder resin (D-2) solution as the binder resin, and M-402 (manufactured by Toagosei Co., Ltd.) as the crosslinking agent (mainly dipentaerythritol hexaacrylate) 9.7 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator A liquid colored composition was prepared by mixing 4.3 parts by mass and 78.4 parts by mass of ethyl 3-ethoxypropionate as a solvent.

Evaluation of withdrawal time The obtained liquid composition was applied on a glass substrate using a spin coater, and then pre-baked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.7 μm. . Next, after cooling the substrate to room temperature, a high-pressure mercury lamp was used for the coating film on the substrate, and radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was applied to each coating film through a photomask at 1,000 J The exposure was performed at an exposure amount of / m ² . Then, shower development was performed by discharging 0.04 mass% potassium hydroxide aqueous solution of 23 degreeC to the coating film on a board | substrate. Under the present circumstances, the time (missing time) until the coating film of an unexposed part peeled completely was measured. The case where the missing time was less than 60 seconds was evaluated as “A”, the case where it was 60 seconds or more and less than 120 seconds was evaluated as “B”, and the case where it was 120 seconds or more was evaluated as “C”. The shorter this time is, the faster the development speed is, and there is an advantage that the tact time for manufacturing the color filter can be shortened. The evaluation results are shown in Table 3.

Evaluation of chromaticity characteristics The obtained colored composition was applied on a glass substrate using a spin coater, and then pre-baked on a hot plate at 100 ° C. for 2 minutes to form three coating films having different film thicknesses. Formed. Next, after these substrates are cooled to room temperature, a high-pressure mercury lamp is used for the coating film on the substrate, and radiation including each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without passing through a photomask. The exposure was performed at an exposure amount of 1,000 J / m ² . Thereafter, post-baking was performed at 220 ° C. for 20 minutes to form a cured film on the substrate. Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the three cured films obtained. (Y) was measured. From the measurement results, the chromaticity coordinate value x and the stimulus value (Y) when the chromaticity coordinate value y = 0.590 were obtained. The evaluation results are shown in Table 3. For Blue, the Y value and x value when the y value was 0.090 were obtained.

Examples 2-14 and Comparative Examples 1-5
Preparation of a colored composition in the same manner as in Example 1 except that the types and amounts of the colorant dispersion, binder resin, crosslinking agent, photopolymerization initiator and solvent were changed as shown in Table 3. And evaluated. The evaluation results are shown in Table 3. In addition, regarding the blue coloring composition (Example 6 and Comparative Example 3), the chromaticity coordinate value x and the stimulation value (Y) at the chromaticity coordinate value y = 0.090 were obtained. The evaluation results are shown in Table 3.

In Table 3, each component is as follows.
C-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name M-402, manufactured by Toagosei Co., Ltd.)
C-2: monoesterified product of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol hexaacrylate, and mixture of dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toagosei Co., Ltd.)
E-1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name IRGACURE OX02, Ciba Specialty・ Made by Chemicals
E-2: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
EEP: ethyl 3-ethoxypropionate MBA: 3-methoxybutyl acetate

Claims (18)

The following components (A), (B) and (C);
(A) a colorant containing a pigment,
(B) A block copolymer having a repeating unit (1) represented by the following formula (1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group. A block copolymer having an A block containing the repeating unit (1) and a B block containing the repeating unit (2) and the repeating unit (3),
(C) contains a crosslinking agent ,
In the block copolymer (B) , the coloring composition for a color filter , wherein a copolymerization ratio of the repeating unit (3) in all repeating units is 0.5 to 15% by mass .

[In Formula (1),
R ¹ represents a hydrogen atom or a methyl group,
Z ^{is, -N + R 2 R 3 R} 4 Y - ( where, R ² to R ⁴ are independently of each other, represent a hydrogen atom, or an optionally substituted hydrocarbon group, Y ^- Represents a counter anion.), —NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ independently of each other represent a hydrogen atom or an optionally substituted hydrocarbon group), or A nitrogen-containing heterocyclic group which may have a substituent;
X ¹ represents a divalent linking group. ]

[In Formula (2),
R ⁷ independently represents an alkylene group having 2 to 4 carbon atoms,
R ⁸ represents an alkyl group having 1 to 6 carbon atoms,
R ⁹ represents a hydrogen atom or a methyl group,
n shows the integer of 1-150. ] The coloring composition for a color filter according to claim 1, wherein in the (B) block copolymer, a copolymerization ratio of the repeating unit (1) in all repeating units is 10 to 60 % by mass. The colored composition for a color filter according to claim 1 or 2, wherein in the (B) block copolymer, a copolymerization ratio of the repeating unit (3) in all repeating units is 1 to 11 % by mass. The coloring composition for color filters according to any one of claims 1 to 3, wherein the acidic group according to the repeating unit (3) is a carboxyl group. In the (B) block copolymer, the copolymerization ratio (A block / B block) of the A block and the B block is 10/90 to 70/30 as a mass ratio. The coloring composition for color filters of Claim 1. The ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn of the (B) block copolymer is 1.0 to 1.8, according to any one of claims 1 to 5 . Coloring composition for color filter. The coloring composition for a color filter according to any one of claims 1 to 6 , further comprising (D) a binder resin (excluding the component (B)). Furthermore (E) a photopolymerization initiator, a color filter coloring composition according to any one of claims 1-7. The coloring composition for a color filter according to any one of claims 1 to 8 , further comprising a dye as a coloring agent. A color filter formed by including a colored layer formed by using the colored composition according to any one of claims 1-9. A color liquid crystal display device comprising the color filter according to claim 10 . The following components (A), (B) and (F);
(A) a colorant containing a pigment,
(B) A block copolymer having a repeating unit (1) represented by the following formula (1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group. A block copolymer having an A block containing the repeating unit (1) and a B block containing the repeating unit (2) and the repeating unit (3),
(F) contains a solvent ,
In the block copolymer (B), a pigment dispersion for a color filter , wherein a copolymerization ratio of the repeating unit (3) in all repeating units is 0.5 to 15% by mass .

[In Formula (1),
R ¹ represents a hydrogen atom or a methyl group,
Z ^{is, -N + R 2 R 3 R} 4 Y - ( where, R ² to R ⁴ are independently of each other, represent a hydrogen atom, or an optionally substituted hydrocarbon group, Y ^- Represents a counter anion.), —NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ independently of each other represent a hydrogen atom or an optionally substituted hydrocarbon group), or A nitrogen-containing heterocyclic group which may have a substituent;
X ¹ represents a divalent linking group. ]

[In Formula (2),
R ⁷ independently represents an alkylene group having 2 to 4 carbon atoms,
R ⁸ represents an alkyl group having 1 to 6 carbon atoms,
R ⁹ represents a hydrogen atom or a methyl group,
n shows the integer of 1-150. ] The pigment dispersion for a color filter according to claim 12 , wherein the solvent (F) contains a solvent (f1) having a hydroxyl group and a solvent (f2) not having a hydroxyl group. 14. The pigment dispersion for a color filter according to claim 13, wherein the mass ratio of the solvent having the (f1) hydroxyl group and the solvent having no (f2) hydroxyl group is 0.5 / 99.5 to 40/60. liquid. In the said (B) block copolymer, the copolymerization ratio of the said repeating unit (1) in all the repeating units is 10-60 mass%, For color filters of any one of Claims 12-14 Pigment dispersion. In the said (B) block copolymer, the copolymerization ratio of the said repeating unit (3) in all the repeating units is 1-11 mass%, For color filters of any one of Claims 12-15 Pigment dispersion. The pigment dispersion for a color filter according to any one of claims 12 to 16, wherein the acidic group according to the repeating unit (3) is a carboxyl group. The said (B) block copolymer WHEREIN: The copolymerization ratio (A block / B block) of the said A block and the said B block is 10 / 90-70 / 30 as mass ratio, Any of Claims 12-17 The pigment dispersion for color filters according to claim 1.