CN102221779B - Color composition for color filter, color filter and color liquid crystal display device - Google Patents

Abstract

The present invention provides a coloring composition for a color filter, a color filter, and a color liquid crystal display element. The coloring composition for a color filter has good chromaticity characteristics, developability, and storage stability, and contains (A) a pigment-containing colorant, (B) an embedded A block copolymer and a C crosslinking agent, the B block copolymer has a repeating unit 1 shown in formula 1, a repeating unit 2 shown in formula 2 and a repeating unit 3 with an acidic group, and has a repeating unit 1 containing The A block and the B block containing repeat unit 2 and repeat unit 3. In Formula 1, R ¹ represents a hydrogen atom or a methyl group, Z represents -N ⁺ R ² R ³ R ⁴ Y ^- , -NR ⁵ R ⁶ or a nitrogen-containing heterocyclic group that may have a substituent, and X ¹ represents a divalent link group. In Formula 2, R ⁷ 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, and n represents an integer of 1 to 150. R ² to R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, and Y- represents a counter anion.

Description

Coloring composition for color filter, color filter, and color liquid crystal display element

technical field

The present invention relates to a coloring composition for a color filter, a color filter, and a color liquid crystal display element, and more specifically, relates to a composition for forming a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, and an electronic paper A coloring composition of a colored layer useful for a color filter used in , etc., a color filter having a colored layer formed using the coloring composition, and a color liquid crystal display element having the color filter.

Background technique

When producing a color filter using a colored radiation-sensitive composition, it is known that after coating a pigment-dispersed colored radiation-sensitive composition on a substrate and drying it, the dried coating film is irradiated with radiation in a desired pattern shape (hereinafter referred to as "exposure") and develop to obtain pixels of each color (Patent Documents 1 and 2). Moreover, the method of forming a black matrix using the photopolymerizable composition in which carbon black was dispersed is also known (patent document 3). Furthermore, there is also known a method of obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition (Patent Document 4).

However, in the field of color filters used for liquid crystal display elements and solid-state imaging elements, pigments used tend to be more and more micronized in response to demands for higher luminance and higher contrast. In order to achieve stable and good dispersibility of such micronized pigments, it is known to be effective to use a dispersant. Various methods of improving the dispersibility of the pigment and improving not only the contrast and dispersion stability but also the developability by using the dispersant have been proposed (Patent Documents 5 to 6).

prior art literature

patent documents

Patent Document 1: Japanese Patent Application Laid-Open No. 2-144502

Patent Document 2: Japanese Patent Application Laid-Open No. 3-53201

Patent Document 3: Japanese Patent Application Laid-Open No. 6-35188

Patent Document 4: Japanese Patent Laid-Open No. 2000-310706

Patent Document 5: Japanese Patent Laid-Open No. 2003-26949

Patent Document 6: Japanese Patent Laid-Open No. 2009-25813

Contents of the invention

However, even with the methods described in these patent documents 5 to 6, it is difficult to realize the requirements for high contrast, high color purity, and high brightness of color liquid crystal display elements in recent years, and it is difficult to say that the amount of color filters can be solved. Various problems such as developability during production. Therefore, development of a coloring composition for color filters that can meet the recent demands for high contrast, high color purity, and high brightness and is excellent in developability is urgently required.

Therefore, an object of the present invention is to provide a coloring composition for color filters which is excellent in chromaticity characteristics and has good developability and storage stability. Furthermore, the object of this invention is to provide the color filter provided with the coloring layer which consists of the said coloring composition, and the color liquid crystal display element provided with this color filter.

In view of this fact, the inventors of the present invention conducted intensive studies, and as a result, found that the above-mentioned problems can be solved by using a block copolymer having a specific repeating unit, and completed the present invention.

That is, the present invention provides a coloring composition for a color filter, characterized in that it contains the following components (A), (B) and (C);

(A) colorants containing pigments;

(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 , and has an A block containing repeating unit (1), and a B block containing repeating unit (2) and repeating unit (3);

(C) Crosslinking agent.

[In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and Z represents -N ⁺ R ² R ³ R ⁴ Y ^- (wherein, R ² to R ⁴ independently represent a hydrogen atom, or may have a substituent Hydrocarbyl, Y ^- represents a counter anion), -NR ⁵ R ⁶ (wherein, R ⁵ and R ⁶ independently represent a hydrogen atom, or a hydrocarbon group that may have a substituent), or a nitrogen-containing heterocyclic group that may have a substituent, X ¹ represents a divalent linking group. ]

[In formula (2), R ⁷ independently represents an alkylene group with 2 to 4 carbon atoms, R ⁸ represents an alkyl group with 1 to 6 carbon atoms, R ⁹ represents a hydrogen atom or a methyl group, and n represents An integer of 1 to 150. ]

Moreover, this invention provides the color filter which has the coloring layer formed using the said coloring composition, and the color liquid crystal display element provided with this color filter. Furthermore, the present invention provides a colorant dispersion for color filters, comprising: a colorant containing the above-mentioned (A) pigment, the above-mentioned (B) block copolymer, and (F) a solvent. Here, the so-called "colored layer" refers to pixels of each color used for a color filter, a black matrix, a black spacer, and the like.

Using the coloring composition of the present invention, a color filter having pixels of each color excellent in chromaticity characteristics 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 can be suitably used for producing color filters for color liquid crystal display elements, color resolution filters for solid-state imaging elements, color filters for organic EL display elements, and electronic paper. Various color filters represented by color filters.

Detailed ways

The present invention will be described in detail below.

Coloring composition for color filter

Hereinafter, the constituent components of the coloring composition for color filters of this invention (henceforth abbreviated as "coloring composition") are demonstrated.

-(A) Colorant-

The coloring composition of this invention contains a pigment as (A) coloring agent. The pigment is not particularly limited, and may be either 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, organic pigments and inorganic pigments can also be used in combination.

Examples of the organic pigments include compounds classified as pigments in the Pigment Index (C.I.; issued by The Society of Dyers and Colourists, Inc.). Specifically, the compound given the following pigment index (C.I.) name can be mentioned.

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

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

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

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 38;

C.I. Pigment Blue 15, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue 60, C.I. Pigment Blue 80;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58;

C.I. Pigment Brown 23, C.I. Pigment Brown 25;

C.I. Pigment Black 1, C.I. Pigment Black 7.

In addition, examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine blue, and Prussian blue. , chromium oxide green, cobalt green, umber, titanium black, synthetic iron black, carbon black, etc.

In the present invention, the pigment can be refined and used by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination of these. In addition, the pigment can be used by modifying the surface of its particles with a resin as needed. As the resin for modifying the particle surface of the pigment, for example, the vehicle resin described in JP-A-2001-1088147 or various commercially available resins for dispersing pigments may be mentioned. As the resin coating method on the surface of carbon black, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, etc. can be used, for example. In addition, the organic pigment is preferably used by making primary particles finer by the so-called salt milling method. As the salt milling method, for example, the method disclosed in JP-A-08-179111 can be used.

In addition, by using a dye as a colorant in the coloring composition for color filters, it becomes possible to achieve high brightness and high contrast that cannot be achieved with a pigment alone. However, when a dye is used as a colorant in a conventional coloring composition, alkali developability remarkably deteriorates (see Comparative Example 4). On the other hand, in the coloring composition of the present invention, by using the (B) block copolymer as a pigment dispersant, alkali developability can be obtained even when a pigment and a dye are combined and used as a colorant. Good coloring composition (cf. Example 14).

As a dye, the compound given the following pigment index (C.I.) name is mentioned, for example.

C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18. C.I. Media Red 7, C.I. Media Yellow 5, C.I. Media Black 7 and other azo dyes;

Anthraquinone dyes such as C.I. Vat Blue 4 (Batutoble-4), C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Disperse Blue 60;

Phthalocyanine dyes such as C.I. bromoindigo 5 (Patdoble-5);

C.I. Basic Blue 3, C.I. Basic Blue 9 and other quinone imine dyes;

C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse Yellow 64 and other quinoline dyes;

C.I. Acid Yellow 1, C.I. Acid Orange 3, C.I. Disperse Yellow 42 and other nitro dyes;

Disperse Yellow 201 and other methazine dyes.

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

From the viewpoint of forming a pixel with high brightness and excellent color purity, or a black matrix with excellent light-shielding properties, the content ratio of the (A) colorant is usually 5 to 70% by mass in the solid content of the coloring composition, preferably 5 to 70% by mass. 60% by mass. Here, the solid content refers to components other than the solvent component described later.

-(B) Block copolymer-

(B) block copolymer in the present invention has repeating unit (1), repeating unit (2) and repeating unit (3), and has the A block that has repeating unit (1), and has repeating unit (2) and the B block of the repeating unit (3) function as a dispersant for the (A) colorant.

The repeating unit (1) is represented by the above formula (1).

In the above formula (1), among a hydrogen atom and a methyl group, a methyl group is preferable as R ¹ .

In addition, Z represents -N ⁺ R ² R ³ R ⁴ Y ^- , -NR ⁵ R ⁶ , or a nitrogen-containing heterocyclic group that may have a substituent, and R ² to R ⁶ independently represent a hydrogen atom or may have a substitution The so-called "hydrocarbon group" in the present invention is a concept including aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group, which can be any form of straight chain, branched and cyclic, and can be saturated in addition. Hydrocarbons may also be unsaturated hydrocarbons, and may have unsaturated bonds at any part of the molecule or terminal.

The above-mentioned aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 (preferably 1 to 12) carbon atoms, more specifically, an alkyl group having 1 to 20 (preferably 1 to 12) carbon atoms, Alkenyl group having 2 to 20 (preferably 2 to 12) carbon atoms, and alkynyl group having 2 to 20 (preferably 2 to 12) carbon atoms. In addition, the above-mentioned alicyclic hydrocarbon is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms (preferably 3 to 12), more specifically, an alicyclic hydrocarbon group having 3 to 20 carbon atoms (preferably 3 to 12) Cycloalkyl. Furthermore, as the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms (preferably 6 to 10) is preferred, and more specifically an aromatic hydrocarbon group having 6 to 20 carbon atoms (preferably 6 to 10) can be mentioned. A group, 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.

Among them, as the hydrocarbon group in R ² to R ⁶ , an alkyl group with 1 to 12 carbon atoms (preferably 1 to 6) and an aralkyl group with 7 to 16 carbon atoms (preferably 7 to 12) are preferred, Particular preference is given to methyl, ethyl, propyl, butyl, benzyl.

In addition, in the present invention, the so-called "nitrogen-containing heterocyclic group" refers to a heterocyclic group having at least one nitrogen atom as a constituent element of the ring, preferably a heteromonocyclic group, or a heterocyclic group formed by condensing two of these Fused heterocyclic group. These heterocyclic groups may be unsaturated rings or saturated rings, and may have heteroatoms other than nitrogen atoms (for example, oxygen atoms, sulfur atoms) in the rings.

Examples of unsaturated heterocyclic rings include pyridine rings, imidazole rings, thiazole rings, Azole ring, triazole ring, imidazoline ring, tetrahydropyrimidine ring, etc. Moreover, as a saturated ring, a morpholine ring, a piperidine ring, a piperazine ring, etc. are mentioned, for example. In addition, as the substituent in the nitrogen-containing heterocyclic group, for example, 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 amido group, a thiol group, sulfide group, etc.

As the above-mentioned heteromonocyclic group, a 5- to 7-membered ring is preferred, and specifically, a group having a basic skeleton represented by the following formula (1-1) or (1-2) can be mentioned, and these heteromonocyclic groups can be It further has a substituent.

In formula (1-1), R represents a hydrogen atom or a hydrocarbon group that may have a substituent, and "*" represents a binding site ( hand), as the hydrocarbon group in R, the same hydrocarbon group as the above ^- mentioned R2 can be mentioned.

In formula (1-2), "*" indicates a binding site.

In addition, specific examples of the condensed heterocyclic group include groups having a basic skeleton represented by the following formulas (1-3) to (1-5), and these heteromonocyclic groups may have a substituent.

In formulas (1-3) to (1-5), "*" represents a binding site.

Examples of the divalent linking group (X ¹ ) in the above formula (1) include a methylene group, an alkylene group having 2 to 10 (preferably 2 to 6) carbon atoms, an arylene group, -CONH-R ¹¹ -group, -COO-R ¹² -group and the like. Here, R ¹¹ and R ¹² are independently a single bond, a methylene group, an alkylene group with 2 to 10 (preferably 2 to 6) carbon atoms, or an ether group with 2 to 10 carbon atoms ( Alkyleneoxyalkylene (alkylenokisialkylenyl). Among them, 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), Y ^- includes halide ions such as Cl ^- , Br ^- , I ^- and acid counter anions 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 kinds of alkylene groups, preferably ethylene and/or propylene.

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.

As R ⁹ , among a hydrogen atom and a methyl group, a methyl group is preferable.

n represents an integer of 1-150, preferably an integer of 1-20, more preferably an integer of 1-10, particularly preferably an integer of 1-5.

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

As a repeating unit (3), the repeating unit represented by following formula (3) is mentioned, for example.

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), among a hydrogen atom and a methyl group, a methyl group is preferable as R ¹⁰ .

Examples of the divalent linking group (X ² ) include a methylene group, an alkylene group having 2 to 10 (preferably 2 to 6) carbon atoms, an arylene group, and a -CONH-R ¹¹ - group. , -COO-R ¹² -group, -OCOR ¹³ -group, -R ¹⁴ -OCO-R ¹⁵ -, -COO-(C _m H _2m COO)lC _m H _2m -group, -COO-R ¹⁶ -OCO- R ¹⁷ - et al. Here, R ¹¹ to R ¹⁵ independently represent 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 ( alkylene oxyalkylene), m represents an integer of 1 to 10, l represents an integer of 1 to ⁴ , R represents a methylene group or an alkylene group with 2 to 10 carbon atoms (preferably 2 to 6) , R ¹⁷ represents a single bond, methylene, an alkylene group with 2 to 10 carbon atoms (preferably 2 to 6), cyclohexane-1,2-diyl or phenylene (for example, 1,2- phenylene, 1,4-phenylene).

Among them, X ² is preferably a single bond, phenylene, -COO-R ¹² -group, -COO-(C _m H _2m COO)lC _m H _2m -group or -COO-R ¹⁶ -OCO-R ¹⁷ - .

(B) The block copolymer may have a repeating unit other than the above (hereinafter referred to as "repeating unit (4)"). Examples of such repeating units (4) include repeating monomers derived from styrene-based monomers such as styrene and α-methylstyrene, (meth)acrylamide, vinyl acetate, and acrylonitrile. unit; a repeating unit represented by the following formula (4). Among them, it is preferable to have a repeating unit represented by the following formula (4) as the repeating unit (4) from the viewpoint of dispersibility. Here, "(meth)acrylate" in this invention 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.

Examples of the hydrocarbon group in R ¹⁸ include the same groups as those for R ² above, and may have the same substituents as for R ² above. Among them, R ¹⁸ is preferably 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, particularly preferably Methyl, ethyl, propyl, butyl, 2-ethylhexyl, phenyl, benzyl, phenylethyl.

(B) The molecular weight of the block copolymer is a weight-average molecular weight (hereinafter also referred to as "Mw") in terms of polymethyl methacrylate measured by gel permeation chromatography (GPC, dissolution solvent: DMF), preferably 1,000 ~30,000, particularly preferably 5,000~15,000. In addition, the ratio (Mw/Mn) of the Mw of the (B) block copolymer to the number average molecular weight (hereinafter also referred to as "Mn") in terms of polymethyl methacrylate measured by GPC (elution solvent: DMF) is preferably 1.0 to 1.8, more preferably 1.0 to 1.7, still more preferably 1.0 to 1.6, particularly preferably 1.0 to 1.3. With such a state of the (B) block copolymer, a colored composition excellent in 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, and it may be an A-B block copolymer It can also be an A-B-A block copolymer.

(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, particularly preferably 15/85 to 60 /30.

In the A block, two or more types of repeating units (1) may be contained in one A block, and at this time, the A block may contain each a repeating unit.

In addition, the B block has, for example, a repeating unit (2) and a repeating unit (3), or has a repeating unit (2), a repeating unit (3) and a repeating unit (4). In the present invention, from the viewpoint of dispersibility , as the B block, preferably has repeating unit (2), repeating unit (3) and repeating unit (4).

The repeating unit constituting the B block may be contained in either random copolymerization or block copolymerization. In addition, two or more types of each repeating unit may be contained in one B block, and in this case, each repeating unit may be contained in the B block in any form of random copolymerization or block copolymerization.

In the (B) 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 still more preferably 15 to 40% by mass of all repeating units. The copolymerization ratio of the repeating unit (2) is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, of the total 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 still more 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, of all the repeating units. By copolymerizing each repeating unit in such a ratio, a colored composition excellent in dispersibility and alkali developability can be obtained.

Such a (B) block copolymer can be produced, for example, by living polymerization of a monomer imparting each of the above-mentioned repeating units. As the living polymerization method, JP-A-9-62002; JP-A-2002-31713; P.Lutz, P.Masson et al, Polym.Bull.12, 79 (1984); BCAnderson, GDAndrews et al. al, Macromolecules, 14, 1601(1981); K.Hatada, K.Ute, et al, Polym.J.17, 977(1985); K.Hatada, K.Ute, et al, Polym.J.18, 1037(1986); Koichi right hand, Koichi Tian, Polymer Processing, 36, 366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46, 189 (1989); M.Kuroki, T.Aida, J.Am.Chem.Soc, 109, 4737(1987); Aida Takuzo, Inoue Shohei, Organic Synthetic Chemistry, 43, 300(1985); DYSogoh, WRHertler et al, Macromolecules, 20, 1473(1987); J.Polym.Sci.Part A Polym.Chem ., 47, 3773-3794 (2009); J. Polym. Sci. Part A Polym. Chem., 47, 3544-3557 (2009) and other known methods described.

As a monomer imparting the repeating unit (1), Z in the formula (1) is -N ⁺ R ² R ³ R ⁴ Y ^- or -NR ⁵ R ⁶ , for example, (meth)acrylic acid Acylaminopropyltrimethylammonium Chloride, (Meth)acryloyloxyethyltrimethylammonium Chloride, (Meth)acryloyloxyethyltrimethylammonium Chloride, (Meth)acryloyloxyethyltrimethylammonium Chloride Ethyl(4-benzoylbenzyl)dimethylammonium bromide, (meth)acryloyloxyethylbenzyldimethylammonium chloride, (meth)acryloyloxyethylbenzyldiethyl Ammonium chloride, Dimethylaminoethyl (meth)acrylate, Diethylaminoethyl (meth)acrylate, Dimethylaminopropyl (meth)acrylate, Diethyl (meth)acrylate Aminopropyl Etc. Furthermore, the repeating unit (1) in which Z is -N ⁺ R ² R ³ R ⁴ Y ^- can also be obtained by, for example, the following method: a monomer (for example, (meth)acrylic acid) in which Z is -NR ⁵ R ⁶ After polymerization of dimethylaminoethyl ester), a halogenated hydrocarbon compound such as benzyl chloride is reacted with the polymer to partially quaternize the amino group.

In addition, as monomers imparting the repeating unit (1), Z in the formula (1) is a nitrogen-containing heterocyclic group, for example, compound group α (monomers 1 to 18) of the following formula, A compound represented by the following formula (5), etc. In addition, the monomers for imparting the repeating unit (1) may be used alone or in combination of two or more.

Compound group α

In addition, examples of monomers imparting the repeating unit (2) include 2-methoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, etc. These can be used individually or in mixture of 2 or more types.

Examples of monomers imparting the repeating unit (3) include (meth)acrylic acid, maleic acid, maleic anhydride, carboxymethyl (meth)acrylate, and 2-carboxyethyl (meth)acrylate. , Mono[2-(meth)acryloyloxyethyl]succinate, ω-carboxypolycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, p-hydroxystyrene, p-hydroxy-α - Methylstyrene, 2-acryloyloxyethylsulfonic acid, 2-methacryloyloxyethylsulfonic acid, sodium 2-acryloyloxyethylsulfonate, 2-acryloyloxyethyl Lithium sulfonate, ammonium 2-acryloyloxyethylsulfonate, imidazole 2-acryloyloxyethylsulfonate Pyridine 2-acryloyloxyethylsulfonate Sodium 2-methacryloyloxyethylsulfonate, lithium 2-methacryloyloxyethylsulfonate, ammonium 2-methacryloyloxyethylsulfonate, 2-methacryloyloxy imidazole ethyl sulfonate Pyridine 2-methacryloyloxyethylsulfonate Styrenesulfonic acid, sodium styrenesulfonate, lithium styrenesulfonate, ammonium styrenesulfonate, imidazole styrenesulfonate Pyridine styrene sulfonate wait. These can be used individually or in mixture of 2 or more types.

In addition, examples of monomers imparting the repeating unit (4) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate Cycropentanil (Meta) Acrylate), isobornyl (meth)acrylate, benzyl (meth)acrylate, phenylethyl (meth)acrylate, and the like. These can be used individually or in mixture of 2 or more types.

(B) The block copolymer can be used individually or in mixture of 2 or more types. Content of (B) 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. If there is too much content of (B) block copolymer, developability may be impaired.

In the present invention, a known dispersant may be further contained in order to improve dispersibility. Examples of known dispersants include polyurethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkylphenyl ether-based dispersants, polyethylene glycol Ester-based dispersants, sorbitan fatty acid ester-based dispersants, fatty acid-modified polyester-based dispersants, acrylic-based dispersants, pigment derivatives, etc.

Specific examples of such dispersants include trade names EFKA (manufactured by EFKA Chemicals b.v. (EFKA)), Disperbyk (manufactured by BYK Chemie (BYK)), Disparlon (manufactured by Kusumoto Chemicals Co., Ltd.), Solsperse (manufactured by Lubrizol Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), EFTOP (Tohkem Products Co., Ltd.), Megaface (Dainippon Ink Chemical Co., Ltd.), Fluorad (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (the above are manufactured by Asahi Glass Co., Ltd.), etc. Moreover, specific examples of pigment derivatives include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quiphthalone.

-(C) Cross-linking agent-

In the present invention, the (C) 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, an N-alkoxymethylamino group, and the like. In this invention, as (C) crosslinking agent, the compound which has 2 or more (meth)acryloyl groups, or the compound which has 2 or more N-alkoxymethylamino groups is preferable.

Specific examples of the compound having two or more (meth)acryloyl groups include polyfunctional (meth)acrylates obtained by reacting aliphatic polyhydroxy compounds with (meth)acrylic acid, caprolactone Modified polyfunctional (meth)acrylates, polyfunctional (meth)acrylates modified by alkenyl oxides, polyfunctional polyurethanes obtained by reacting (meth)acrylates with hydroxyl groups with polyfunctional isocyanates ( Meth)acrylates, polyfunctional (meth)acrylates having carboxyl groups obtained by reacting (meth)acrylates having hydroxyl groups with acid anhydrides, etc.

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, An aliphatic polyol compound having a valence of three or more, such as dipentaerythritol. Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, Dipentaerythritol penta(meth)acrylate, glycerin dimethacrylate, etc. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, etc. are mentioned, for example. Examples of acid anhydrides include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, Tetrabasic acid dianhydrides such as biphenyltetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride.

In addition, examples of the caprolactone-modified polyfunctional (meth)acrylate include compounds described in paragraphs [0015] to [0018] of JP-A-11-44955. Examples of the polyfunctional (meth)acrylate modified with the above-mentioned alkylene oxide include ethylene oxide and/or propylene oxide modified di(meth)acrylate of bisphenol A, isocyanuric acid Ethylene oxide and/or propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide and/or propylene oxide modified tri(meth)acrylate, pentaerythritol ring Ethylene oxide and/or propylene oxide modified tri(meth)acrylate, ethylene oxide and/or propylene oxide modified tetra(meth)acrylate of pentaerythritol, ethylene oxide and/or dipentaerythritol Or propylene oxide modified penta(meth)acrylate, ethylene oxide and/or propylene oxide modified hexa(meth)acrylate of dipentaerythritol, etc.

Moreover, as a compound which has 2 or more of said N-alkoxymethyl amino groups, the compound etc. which have a melamine structure, a benzoguanamine structure, a urea structure etc. are mentioned, for example. It should be noted that the so-called melamine structure and benzoguanamine structure refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as the basic skeleton, and include melamine, benzoguanamine or these The concept of condensation. Specific examples of compounds having two or more N-alkoxymethylamino groups include N,N,N,N,N,N-hexa(alkoxymethyl)melamine, N,N,N , N-tetra(alkoxymethyl) phenylguanamine, N, N, N, N-tetra(alkoxymethyl) glycoluril, etc.

Among these polyfunctional monomers, polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyols with (meth)acrylic acid, caprolactone-modified polyfunctional (meth) Acrylates, polyfunctional urethane (meth)acrylates, polyfunctional (meth)acrylates with carboxyl groups, N,N,N,N,N,N-hexa(alkoxymethyl)melamine, N,N , N, N-tetrakis(alkoxymethyl)phenylguanamine. From the viewpoints that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and it is difficult to generate dirt (ground stain れ) and film residue on the substrate of the unexposed part and the light-shielding layer, the aliphatic layer having a trivalent or more Among polyfunctional (meth)acrylates obtained by reacting polyols with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. , Among polyfunctional (meth)acrylates having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride are particularly preferable.

In this invention, (C) crosslinking agent can be used individually or in mixture of 2 or more types.

The content of the (C) crosslinking agent in the present invention is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass, relative to 100 parts by mass of the (A) colorant. At this time, 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 multifunctional monomer is too large, when alkali developability is imparted to the coloring composition of the present invention, alkali developability will decrease, and it will easily occur on the substrate of the unexposed portion or on the light-shielding layer. Tendency to foul, film residue, etc.

-(D) Binder resin-

The colored composition of the present invention may contain (D) a binder resin. Thereby, the alkali developability of a coloring composition, and the adhesiveness to a board|substrate can be improved. 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, polymers having carboxyl groups (hereinafter referred to as "carboxyl group-containing polymers") are preferred, and examples include ethylenically unsaturated monomers having one or more carboxyl groups (hereinafter referred to as "unsaturated monomers (d1) ”) and other polymerizable 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]ester, ω-carboxy Polycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, etc.

These unsaturated monomers (d1) can be used individually or in mixture of 2 or more types.

In addition, examples of the above-mentioned unsaturated monomer (d2) include:

N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide; styrene, alpha-methylstyrene, p-hydroxystyrene, p-hydroxy-alpha -Aromatic vinyl compounds such as methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene;

Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, ( Benzyl methacrylate, polyethylene glycol (n = 2 ~ 10) methyl ether (meth) acrylate, polypropylene glycol (n = 2 ~ 10) methyl ether (meth) acrylate, polyethylene glycol ( n=2～10) mono(meth)acrylate, polypropylene glycol (n=2～10) mono(meth)acrylate, (meth)cyclohexyl acrylate, (meth)isobornyl acrylate, three Cyclo[ ^5.2.1.02,6 ]decane-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, (meth)acrylate 4- Hydroxyphenyl ester, ethylene oxide modified (meth)acrylate of p-cumenylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3- (Meth)acrylic acid such as [(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane ester;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl yl)-Vinyl ethers such as 3-ethyloxetane;

Polymer chains such as polystyrene, polymethyl(meth)acrylate, poly(n-butylmeth)acrylate, polysiloxane, and macromonomers with a single (meth)acryloyl group at the end .

These unsaturated monomers (d2) can be used individually or in mixture of 2 or more types.

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 10 to 40% by mass. quality%. By copolymerizing the unsaturated monomer (d1) within such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

Specific examples of copolymers of unsaturated monomers (d1) and unsaturated monomers (d2) include, for example, Japanese Patent Application Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10- 31308, JP-A-10-300922, JP-11-174224, JP-11-258415, JP-2000-56118, JP-2004-101728, etc. copolymer.

In addition, in the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-09-325494, JP-11 -140144A, JP-A-2008-181095, etc. disclose that a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth)acryloyl group in a side chain is used as a binder resin.

The weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) of the binder resin in the present invention is usually 1,000-100,000, preferably 3,000-50,000. If the weight-average molecular weight is too small, the remaining film ratio of the obtained film may be reduced, or the pattern shape, heat resistance, etc. may be damaged, and the electrical characteristics may be deteriorated. On the other hand, if it is too large, the resolution may be reduced. Or the shape of the pattern is damaged, and dry foreign matter is likely to be generated when coating with a slit nozzle method.

In addition, in the present invention, the ratio (weight average molecular weight/number average molecular weight) of the weight average molecular weight of the binder resin to the polystyrene-equivalent number average molecular weight measured by GPC (elution solvent: tetrahydrofuran) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

The binder resin in the present invention can be produced by a known method, and for example, those disclosed in JP 2003-222717 A, JP 2006-259680 A, International Publication No. 07/029871 pamphlet, etc. can be used. Methods to control its structure, weight average molecular weight, weight average molecular weight/number average molecular weight.

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) colorants, Preferably it is 20-500 mass parts. If the content of the binder resin is too small, for example, the alkali developability may be reduced, or the storage stability of the obtained coloring composition may be reduced. The target color density may become difficult.

-(E) Photopolymerization initiator-

(E) The photoinitiator may be contained in the coloring composition of this invention. Thereby, radiation sensitivity can be provided to a coloring composition. The (E) photopolymerization initiator used in the present invention is a compound capable of generating an active species capable of initiating polymerization of the above-mentioned (C) crosslinking agent by exposure to radiation such as visible rays, ultraviolet rays, extreme ultraviolet rays, electron beams, and X-rays.

Examples of such photopolymerization initiators include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyl oxime-based compounds, Salt-based compounds, benzoin-based compounds, benzophenone-based compounds, α-diketone-based compounds, polycyclic quinone-based compounds, diazo-based compounds, imidesulfonate-based compounds, and the like.

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-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, and O-acyloxime-based compounds.

Among preferable photopolymerization initiators in the present invention, specific examples of thioxanthone-based compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone. Ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Thioxanthone, etc.

In addition, specific examples of the aforementioned acetophenone-based compounds 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, etc.

In addition, specific examples of the above-mentioned biimidazole-based compounds 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)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc.

In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable to use a hydrogen donor together because sensitivity can be improved. The "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole-based compound by exposure. As the hydrogen donor, for example, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, Thiol-based hydrogen donors such as azoles, and amine-based hydrogen donors such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used alone or in combination of two or more. From the viewpoint of further improving the sensitivity, it is preferable to use a combination of one or more thiol-based hydrogen donors and one or more amine-based hydrogen donors. .

In addition, specific examples of the above-mentioned triazine compounds include 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, oxazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethene Base]-4,6-bis(trichloromethyl)-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloro Methyl)-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-triazine, 2-(4-methoxy phenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2- Triazine compounds having a halomethyl group such as (4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.

In addition, specific examples of O-acyl oxime compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime), Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethyl ketone, 1-[ 9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethyl ketone, 1 -[9-Ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazole-3 -Base]-, 1-(O-acetyl oxime) and so on.

In the present invention, when photopolymerization initiators other than biimidazole-based compounds such as acetophenone-based compounds are used, a sensitizer may be used in combination. Examples of such sensitizers include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylamino Aminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethyl (aminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc.

In this invention, 0.01-120 mass parts of content of a photoinitiator is preferable with respect to 100 mass parts of (C) crosslinking agents, Especially preferably, it is 1-100 mass parts. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may become insufficient, while if it is too large, the formed colored layer tends to be easily detached from the substrate during development.

-(F)Solvent-

The coloring composition of the present invention can usually be prepared by mixing a colorant containing (A) a pigment, (B) a block copolymer, and other dispersants as needed in (F) a solvent. , (D) A part of the binder resin is pulverized, mixed, and dispersed using a bead mill, a roll mill, etc. to prepare a pigment dispersion, and then, the (C) crosslinking agent, It is mixed with (D) binder resin, (E) photopolymerization initiator, further added (F) solvent, etc. added as needed. As the solvent (F), it can be appropriately selected and used as long as it disperses or dissolves components (A) to (C) and other components constituting the coloring composition, does not react with these components, and has moderate volatility. However, from the viewpoint of dispersibility and stability, it is preferable to use together (f1) a solvent having a hydroxyl group (hereinafter also referred to as "solvent (f1)") and (f2) a solvent not having a hydroxyl group ( Hereinafter, it is also referred to as "solvent (f2)").

Among such solvents, examples of the solvent (f1) include 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 Ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono Diethyl ether and other (poly) alkylene glycol monoalkyl ethers;

Lactate alkyl esters such as methyl lactate and ethyl lactate;

Methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol and other (cyclo)alkyl alcohols;

Ketone alcohols such as diacetone alcohol, etc.

Among 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.

In addition, examples of the solvent (f2) include 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, 3-methyl-3-methoxybutyl ethyl (poly)alkylene glycol monoalkyl ether acetates such as acid esters;

Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers;

Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones;

Diacetates such as propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, etc.;

Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methoxypropionate Alkoxy carboxylates such as -3-methoxybutyl propionate;

Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate , isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate and other esters kind;

Aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

Among these solvents (f2), preferred are (poly)alkylene glycol monoalkyl ether acetates, ethers, ketones, diacetates, alkoxy carboxylates, particularly preferably ethylene glycol monomethyl ether Ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether acetate, diglyme, Glycol methyl ethyl ether, cyclohexanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl 3-methoxypropionate, 3-ethoxypropane Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate. The solvent (f2) can be used individually or in mixture of 2 or more types.

In the present invention, the mass 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, especially Preferably 5/95～25/75.

The content of the solvent is not particularly limited, and whether it is a pigment dispersion or a coloring composition, the total concentration of each component excluding the solvent of the pigment dispersion or coloring composition is preferably 5 to 50% by mass, particularly preferably 10% by mass. ~40% by mass. In such a state, a colored dispersion liquid with good dispersibility and stability, and a colored composition with good applicability and stability can be obtained.

-additive-

The coloring composition of the present invention may contain various additives as necessary.

Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicon-based surfactants; Trimethoxysilane, Vinyltriethoxysilane, Vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidol Oxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethyl Oxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and other adhesion promoters; 2,2-thiobis(4-methyl-6-tert Butylphenol), 2,6-di-tert-butylphenol and other antioxidants; 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, alkoxy UV absorbers such as benzophenones; anti-aggregating agents such as sodium polyacrylate; 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-butanediol and other residue improvers ;Mono[2-(meth)acryloyloxyethyl]succinate, mono[2-(meth)acryloyloxyethyl]phthalate, ω-carboxypolycaprolactone mono(form base) developability improver such as acrylate, etc.

Color filter and manufacturing method thereof

The color filter of this invention has the coloring layer formed using the coloring composition of this invention.

As a method of manufacturing a color filter, the following methods are mentioned first. First, a light-shielding layer (black matrix) is formed as necessary on the surface of the substrate to partition portions where pixels are formed. Next, after coating the liquid composition of the radiation-sensitive composition dispersed with, for example, a red colorant on the substrate, prebaking is performed to evaporate the solvent to form a coating film. Next, after exposing this coating film through a photomask, it develops using an alkali developing solution, and dissolves and removes the unexposed part of a coating film. Then, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

Next, using each colored radiation-sensitive composition of green or cyan, coating, pre-baking, exposure, development, and post-baking of each colored radiation-sensitive composition were carried out in the same manner as above, and green color was sequentially formed on the same substrate. The pixel array and the cyan pixel array. In this way, a color filter in which a pixel array of three primary colors of red, green, and cyan is arranged on a substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order.

In addition, the black matrix can be formed by making a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern by photolithography, but it is also possible to use a colored radiation-sensitive composition in which a black colorant is dispersed, It is formed in the same manner as when forming the above-mentioned pixels.

Examples of the substrate used when forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide-imide, and polyimide.

In addition, these substrates may be subjected to appropriate pretreatments such as reagent treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, and vacuum deposition as necessary.

When coating the colored radiation-sensitive composition on the substrate, appropriate coating methods such as spray method, roll coating method, spin coating method (spin coating method), slot die coating method, and bar coating method can be used, In particular, spin coating and slot die coating are preferably used.

Prebaking is usually carried out by combining drying under reduced pressure and drying under heat. Drying under reduced pressure is usually carried out until it reaches 50 to 200 Pa. Moreover, the conditions of heat drying are drying at 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 a film thickness after drying.

Examples of radiation sources used for forming pixels and/or black matrices include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps. Lamp light source, argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser, etc., but radiation with a wavelength in the range of 190 to 450 nm is preferable.

Generally, the exposure dose of radiation is preferably 10 to 10,000 J/m ² .

In addition, as the above-mentioned alkaline developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecane, Aqueous solutions of alkenes, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc.

An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the above-mentioned alkaline developing solution. In addition, washing with water is usually performed after alkali image development.

As the developing treatment method, a shower developing method, a spray developing method, a immersion developing method, a immersion (liquid-covered) developing method, etc. can be used. Image development conditions are preferably carried out at normal temperature for 5 to 300 seconds.

The post-baking conditions are usually about 10 to 60 minutes at 180 to 280°C.

The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

In addition, as a second method of manufacturing a color filter, a method of obtaining pixels of each color by an inkjet method disclosed in JP-A-7-318723 and JP-A-2000-310706 is also known. In this method, first, partition walls having a light-shielding function are formed on the surface of the substrate. Next, a liquid composition in which a coloring composition such as a red colorant is dispersed is ejected into the formed partition walls by an inkjet device, and then prebaking is performed to evaporate the solvent. Next, after exposing the coating film as necessary, it is cured by post-baking to form a red pixel pattern.

Next, using each coloring composition of green or cyan, a green pixel pattern and a cyan pixel pattern were sequentially formed on the same substrate in the same manner as above. Thus, a color filter in which pixel patterns of three primary colors of red, green, and cyan are simultaneously arranged on a substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order.

In addition, the barrier ribs not only have a light-shielding function, but also function to prevent color mixing of the coloring compositions discharged into the partitions, and therefore are thicker than the black matrix film used in the first method. Therefore, the partition wall is usually formed using a black radiation-sensitive composition.

The substrate used for forming the color filter, the source of radiation, and the methods and conditions of pre-baking and post-baking are the same as those of the above-mentioned first method. In this way, the film thickness of the pixel formed by the inkjet method is about the same as the thickness of the black matrix.

On the pixel pattern obtained in this way, after forming a protective film as needed, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. Usually, the spacer can be formed using a radiation-sensitive composition, but it can also be made into a light-shielding spacer (black spacer). At this time, the colored composition of the present invention can also be favorably used for the formation of the black spacer by using a colored radiation-sensitive composition in which a black colorant is dispersed.

The color filter of the present invention thus obtained is extremely high in luminance and color purity, and therefore is extremely useful for color liquid crystal display devices, color image pickup tube devices, color sensors, organic EL display devices, electronic paper, and the like.

Color liquid crystal display element

The color liquid crystal display element of this invention is equipped with the color filter of this invention.

The color liquid crystal display element of the present invention can take an appropriate structure. For example, it is possible to adopt a structure in which a color filter is formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed face each other through a liquid crystal layer. Further, it is also possible to adopt: A structure in which a substrate on which a color filter is formed on the surface of a driving substrate on which a thin-film transistor (TFT) is disposed faces a substrate on which an ITO (tin-doped indium oxide) electrode is formed via a liquid crystal layer. The latter structure has the advantages of being able to significantly increase the aperture ratio and obtain a bright and high-definition liquid crystal display element.

The color liquid crystal display device of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp). As the white LED, for example, a white LED that obtains white light by using a red LED, a green LED, and a cyan LED having independent spectra, a white LED that obtains white light by combining a red LED, a green LED, and a cyan LED through color mixing, and a combination of A white LED that obtains white light by mixing colors of a cyan LED, a red LED, and a green phosphor, and a white LED that obtains white light by combining a cyan LED, a red phosphor, and a green phosphor by mixing colors, and color mixing of a cyan LED and a YAG-based phosphor For white LEDs that obtain white light, white LEDs that combine cyan LEDs, orange phosphors, and green phosphors to obtain white light through color mixing, and ultraviolet LEDs, red phosphors, green phosphors, and cyan phosphors to obtain white light through color mixing of white LEDs etc.

The color liquid crystal display element of the present invention can be applied to TN (Twisted Nematic, twisted nematic) type, STN (Super Twisted Nematic, super twisted nematic) type, IPS (In-Planes Switching, in-plane switching) type, VA (Vertical Alignment, Vertical alignment) type, OCB (Optically Compensated Birefringence, optically compensated bending alignment) type and other suitable liquid crystal types.

Example

Examples are given below to further specifically describe the embodiment of the present invention. However, the present invention is not limited to the following examples.

<(B) Synthesis of Block Copolymer>

Synthesis Example 1

In a flask equipped with a stirring bar, 1.4 g of methacrylic acid (hereinafter referred to as "MA") and 5.6 g of methoxypolyethylene glycol monomethacrylate (PME-200, manufactured by NOF Corporation) were mixed. (hereinafter referred to as "PME-200"), 5.0 g of n-butyl methacrylate (hereinafter referred to as "nBMA"), 5.0 g of 2-ethylhexyl methacrylate (hereinafter referred to as "EHMA"), 1.7g of benzyl methacrylate (hereinafter referred to as "BzMA"), 7.8g of methyl methacrylate (hereinafter referred to as "MMA"), 303mg of 2,2'-azobisisobutyronitrile (hereinafter referred to as "AIBN") and 781 mg of pyrazole-1-dithiocarboxylate cyano(dimethyl)methyl ester were dissolved in 30 mL of toluene, and nitrogen bubbles were performed for 30 minutes. Thereafter, the reaction solution was stirred slowly to raise the temperature of the reaction solution to 60° C., and the temperature was maintained for 24 hours to perform living radical polymerization.

Next, 73 mg of AIBN and 1.4 g of dimethylaminoethyl methacrylate (hereinafter referred to as "DAMA") were dissolved in 20 mL of toluene, nitrogen replacement was performed for 30 minutes, and the resulting solution was added to the above In the reaction solution, living radical polymerization was performed at 60° C. for 24 hours. Then, 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, a block copolymer solution comprising A blocks having repeating units derived from DAMA and B blocks having repeating units derived from MA, PME-200, nBMA, EHMA, BzMA, and MMA was obtained. Let the obtained block copolymer be "block copolymer (B-1)".

Synthesis example 2

In a flask equipped with a stirring 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-dithiocarboxylate cyano(dimethyl)formazol The ester was dissolved in 30 mL of toluene and nitrogen bubbles were carried out for 30 minutes. Thereafter, the reaction solution was stirred slowly to raise the temperature of the reaction solution to 57° C., and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, 277 mg of AIBN and 5.3 g of DAMA were dissolved in 20 mL of toluene, nitrogen substitution was performed for 30 minutes, the resulting solution was added to the above reaction solution, and living radical polymerization was performed at 57° C. for 34 hours. Then, 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, a block copolymer comprising an A block with repeating units derived from DAMA and a B block with repeating units derived from MA, PME-200 and nBMA was obtained. Let the obtained block copolymer be "block copolymer (B-2)".

Synthesis example 3

In a flask equipped with a stirring 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 was dissolved in 30 mL of toluene, and nitrogen gas was bubbled for 30 minutes. Thereafter, the reaction solution was stirred slowly to raise the temperature of the reaction solution to 60° C., and the temperature was maintained for 24 hours to perform living radical polymerization.

Next, 277 mg of AIBN and 16.2 g of DAMA were dissolved in 20 mL of toluene, nitrogen substitution was performed for 30 minutes, the resulting solution was added to the reaction solution, and living radical polymerization was performed at 60° C. for 24 hours. Then, 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, block copolymers were obtained comprising A blocks with repeating units derived from DAMA and B blocks with repeating units derived from MA, PME-200, nBMA and MMA. The obtained block copolymer is referred to as "block copolymer (B-3)".

Synthesis Example 4

In a flask equipped with a stirring 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-dithiocarboxylate cyano ( Dimethyl)methyl ester was dissolved in 30 mL of toluene, and nitrogen gas was bubbled for 30 minutes. Thereafter, the reaction solution was stirred slowly to raise the temperature of the reaction solution to 60° C., and the temperature was maintained for 24 hours to perform living radical polymerization.

Next, 946 mg of AIBN and 18.2 g of DAMA were dissolved in 20 mL of toluene, nitrogen substitution was performed for 30 minutes, the resulting solution was added to the above reaction solution, and living radical polymerization was performed at 60° C. for 24 hours. Then, 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, a block copolymer comprising an A block with repeating units derived from DAMA and a B block with repeating units 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 stirring 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-dithiocarboxylate cyano(dimethyl)formazol The ester was dissolved in 30 mL of toluene and nitrogen bubbles were carried out for 30 minutes. Thereafter, the reaction solution was stirred slowly to raise the temperature of the reaction solution to 57° C., and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, 306 mg of AIBN and 5.9 g of DAMA were dissolved in 20 mL of toluene, nitrogen substitution was performed for 30 minutes, the resulting solution was added to the reaction solution, and living radical polymerization was performed at 57° C. for 34 hours. Then, 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, a block copolymer comprising an A block with repeating units derived from DAMA and a B block with repeating units derived from MA, PME-200 and nBMA was obtained. The obtained block copolymer was referred to as "block copolymer (B-5)".

Synthesis Example 6

In a flask equipped with a stirring 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 768 mg of pyrazole- Cyano(dimethyl)methyl 1-dithiocarboxylate was dissolved in 30 mL of toluene, and nitrogen gas was bubbled for 30 minutes. Thereafter, the reaction solution was stirred slowly to raise the temperature of the reaction solution to 57° C., and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, 336 mg of AIBN and 5.9 g of DAMA were dissolved in 20 mL of toluene, nitrogen substitution was performed for 30 minutes, the resulting solution was added to the reaction solution, and living radical polymerization was performed at 57° C. for 34 hours. Then, 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, block copolymers were obtained comprising A blocks with repeat units derived from DAMA and B blocks with repeat units derived from MA, PME-200, nBMA, EHMA, BzMA and MMA. Let the obtained block copolymer be "block copolymer (B-6)".

Synthesis Example 7

In a flask equipped with a stirring 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-dithiocarboxylate cyano(dimethyl)formazol The ester was dissolved in 30 mL of toluene and nitrogen bubbles were carried out for 30 minutes. Thereafter, the reaction solution was stirred slowly to raise the temperature of the reaction solution to 60° C., and the temperature was maintained for 24 hours to perform living radical polymerization.

Next, 306 mg of AIBN and 5.9 g of DAMA were dissolved in 20 mL of toluene, nitrogen substitution was performed for 30 minutes, the resulting solution was added to the above reaction solution, and living radical polymerization was performed at 60° C. for 24 hours. Then, 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, a block copolymer comprising an A block with repeating units derived from DAMA and a B block with repeating units derived from MA, PME-200 and nBMA was obtained. The obtained block copolymer was referred to as "block copolymer (B-7)".

Synthesis Example 8

In a flask equipped with a stirring 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 856 mg of pyrazole- Cyano(dimethyl)methyl 1-dithiocarboxylate was dissolved in 30 mL of toluene, and nitrogen gas was bubbled for 30 minutes. Thereafter, the reaction solution was stirred slowly to raise the temperature of the reaction solution to 60° C., and the temperature was maintained for 24 hours to perform living radical polymerization.

Next, 291 mg of AIBN and 5.6 g of DAMA were dissolved in 20 mL of toluene, nitrogen substitution was performed for 30 minutes, the resulting solution was added to the above reaction solution, and living radical polymerization was performed at 60° C. for 24 hours. Then, 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, block copolymers were obtained comprising A blocks with repeat units derived from DAMA and B blocks with repeat units derived from MA, PME-200, nBMA, EHMA, BzMA and MMA. The obtained block copolymer was referred to as "block copolymer (B-8)".

Synthesis Example 9

In a flask equipped with a stirring bar, 1.4 g of MA, 1.9 g of PME-200, 3.5 g of nBMA, 3.5 g of EHMA, 1.6 g of BzMA, 7.2 g of MMA, 337 mg of AIBN and 621 mg of pyrazole- Cyano(dimethyl)methyl 1-dithiocarboxylate was dissolved in 30 mL of toluene, and nitrogen gas was bubbled for 30 minutes. Thereafter, the reaction solution was stirred slowly to raise the temperature of the reaction solution to 62° C., and the temperature was maintained for 20 hours to perform living radical polymerization.

Next, 640 mg of AIBN and 8.8 g of DAMA were dissolved in 20 mL of toluene, nitrogen substitution was performed for 30 minutes, the resulting solution was added to the above reaction solution, and living radical polymerization was performed at 62° C. for 20 hours. Then, 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, block copolymers were obtained comprising A blocks with repeat units derived from DAMA and B blocks with repeat units derived from MA, PME-200, nBMA, EHMA, BzMA and MMA. The obtained block copolymer was referred to as "block copolymer (B-9)".

Synthesis Example 10

In a flask equipped with a stirring bar, 1.4 g of MA, 7.3 g of PME-200, 5.6 g of nBMA, 2.8 g of EHMA, 1.5 g of BzMA, 1.5 g of MMA, 197 mg of AIBN and 507 mg of pyrazole- Cyano(dimethyl)methyl 1-dithiocarboxylate was dissolved in 30 mL of toluene, and nitrogen gas was bubbled for 30 minutes. Thereafter, the reaction solution was stirred slowly to raise the temperature of the reaction solution to 57° C., and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, 312 mg of AIBN and 7.8 g of monomer-1 were dissolved in 20 mL of toluene, nitrogen replacement was carried out for 30 minutes, the resulting solution was added to the above reaction solution, and the activity free reaction was carried out at 57° C. for 34 hours. base aggregation. Then, 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, a block copolymer comprising A blocks with repeating units from Monomer-1 and B blocks with repeating units from MA, PME-200, nBMA, EHMA, BzMA and MMA was obtained. Let the obtained block copolymer be "block copolymer (B-10)".

Synthesis Example 11

594.35 g of tetrahydrofuran (hereinafter referred to as "THF") and 10.98 g of lithium chloride (3.63% by mass THF solution) were placed in the flask, and cooled to -60°C. Then, 7.89 g of n-butyllithium (15.36% by mass concentration of hexane solution) was added, followed by aging for 10 minutes.

Next, a mixture of 4.04 g of 1-ethoxyethyl methacrylate (hereinafter referred to as "EEMA"), 61.33 g of nBMA, and 26.19 g of PME-200 was added dropwise over 30 minutes, and the reaction was continued after dropping 30 minutes. Then, the disappearance of the monomer was confirmed by measuring by gas chromatography (hereinafter referred to as "GC")·GPC (mobile phase THF, DMF).

Next, 39.71 g of DAMA was dripped, and reaction was continued for 30 minutes after dripping. Then, after measuring by GC·GPC (mobile phase DMF) and confirming the disappearance of the monomer, 3.21 g of methanol was added to stop the reaction.

200 g of a 50 mass % concentration of propylene glycol monomethyl ether acetate solution of the obtained precursor copolymer was heated to 160° C. for 3 hours to deprotect EEMA. Then, by adding propylene glycol monomethyl ether acetate, the non-volatile content was adjusted to 40% by mass. Thus, a block copolymer comprising an A block with repeating units derived from DAMA and a B block with repeating units derived from MA, PME-200 and nBMA was obtained. The obtained block copolymer was referred to as "block copolymer (B-11)".

Synthesis Example 12

578.66 g of THF and 11.20 g of lithium chloride (3.63% by mass THF solution) were added to the flask, and cooled to -60°C. Then, 7.34 g of n-butyllithium (15.36% by mass concentration of hexane solution) was added, followed by aging for 10 minutes.

Then, 4.30 g of MMA was added, and reaction was continued for 5 minutes. Then, after confirming the disappearance of the monomer by GC measurement, a part of the sample was sampled for GPC measurement, and a polymer having a molecular weight of 293 (2.92-mer) was produced.

Next, a mixture of 4.52g of EEMA, 19.80g of EHMA, 19.50g of nBMA, 36.48g of MMA, 15.03g of BzMA, and 11.99g of PME-200 was added dropwise over 30 minutes, and the reaction was continued for 30 minutes after dropping . Disappearance of monomers was then confirmed by GC·GPC (mobile phase THF, DMF) measurement.

Next, 36.98 g of DAMA was dripped, and reaction was continued for 30 minutes after dripping. Then, after confirming the disappearance of the monomer by GC·GPC (mobile phase DMF) measurement, 3.21 g of methanol was added to stop the reaction.

200 g of a 50 mass % concentration of propylene glycol monomethyl ether acetate solution of the obtained precursor copolymer was heated to 160° C. for 3 hours to deprotect EEMA. Then, by adding propylene glycol monomethyl ether acetate, the non-volatile content was adjusted to 40% by mass. Thus, block copolymers were obtained comprising A blocks with repeat units derived from DAMA and B blocks with repeat units derived from MA, PME-200, nBMA, EHMA, BzMA and MMA. The obtained block copolymer was referred to as "block copolymer (B-12)".

Comparative Synthesis Example 1

558.67 g of THF and 0.28 g of lithium chloride (3.63% by mass THF solution) were added to the flask, and cooled to -60°C. Then, 7.60 g of n-butyllithium (15.36% by mass concentration of hexane solution) was added and aged for 10 minutes.

Then, 4.38 g of MMA was added, and reaction was continued for 5 minutes. Then, after confirming the disappearance of the monomer by GC measurement, a part was sampled and subjected to GPC measurement, and a polymer having a molecular weight of 346 (3.46-mer) was produced.

Next, a mixed solution of 17.08 g of EHMA, 16.95 g of nBMA, 31.66 g of MMA, 8.01 g of BzMA, and 9.48 g of PME-200 was added dropwise over 30 minutes, and the reaction was continued for 30 minutes after the dropwise addition. Disappearance of monomers was then confirmed by GC·GPC (mobile phase THF, DMF) measurement.

Next, 42.98 g of DAMA was dripped, and reaction was continued for 30 minutes after dripping. Then, after confirming the disappearance of the monomer by GC·GPC (mobile phase DMF) measurement, 2.40 g of methanol was added to stop the reaction. Then, 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, block copolymers were obtained comprising A blocks with repeat units derived from DAMA and B blocks with repeat units derived from PME-200, nBMA, EHMA, BzMA and MMA. Let the obtained block copolymer be "block copolymer (b-1)".

Comparative Synthesis Example 2

In a flask equipped with a stirring bar, 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 pyrazole-1-dithiocarboxylic acid cyano (dimethyl 579 mg of methyl ester was dissolved in 50 mL of toluene, and nitrogen gas was blown for 30 minutes. Thereafter, the reaction solution was stirred slowly to raise the temperature of the reaction solution to 57° C., and the temperature was maintained for 34 hours to perform living radical polymerization.

Then, 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, random copolymers with repeating units from MA, PME-200, nBMA and DAMA were 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 as follows. In Table 1, measurement results are shown together with the copolymerization ratio (mass %) of each monomer in (B) block copolymer.

Apparatus: GPC-104 (manufactured by Showa Denko Co., Ltd.).

Column: Use KD-G, KF-603, KF-602, and KF-601 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 in the following manner. The measurement results are shown in Table 1.

0.5 g of the block copolymer solution was precisely weighed to a unit of 1 mg, and divided into glass containers. After diluting to 50 mL with propylene glycol monomethyl ether acetate, phenolphthalein was added and titrated with a 0.1N ethanolic potassium hydroxide aqueous solution, and the point where it was colored pink was defined as an end point. A blank test was also carried out. The acid value (unit: mgKOH/g) was calculated from (B) the block copolymer and the amount of 0.1N ethanolic potassium hydroxide solution dropped in the blank test. It should be noted that the acid value in the present invention represents the number of milligrams of KOH required to neutralize 1 g of the nonvolatile components of the solvent excluding the block copolymer solution.

<Determination of amine value>

The amine value of the (B) block copolymer obtained in each of the above synthesis examples was measured in the following manner. The measurement results are shown in Table 1.

0.5 g of the block copolymer solution was precisely weighed to a unit of 1 mg, and divided into glass containers. 20 mL of acetic anhydride/acetic acid=9/1 (volume ratio) was added and dissolved, and it was left to stand at room temperature for 3 hours. Then, after further adding 30 mL of acetic acid, titration was performed with a 0.1 mol/L perchloric acid·acetic acid solution using a potential difference measuring device AT-510 (manufactured by Kyoto Denshi Kogyo Co., Ltd.). A blank test was also carried out. The amine value (unit: mgKOH/g) was calculated from (B) the block copolymer and the 0.1 mol/L perchloric acid·acetic acid solution dripped into the blank test. The amine value in the present invention represents the number of milligrams of KOH equivalent to the acid required to neutralize 1 g of the nonvolatile components of the solvent excluding the block copolymer solution.

Table 1

<Preparation of colorant dispersion>

Modulation Example 1

9 parts by mass of C.I. Pigment Green 58 (manufactured by DIC Corporation), 6 parts by mass of C.I. Pigment Yellow 150, and 12.5 parts by mass of a block copolymer (B-1) solution (non-volatile content = 40% by mass) were used as colorants. ), 64.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and 8 parts by mass of propylene glycol monomethyl ether were processed using a bead mill to prepare a colorant dispersion (A-1).

Modulation Examples 2-14 and Comparative Modulation Examples 1-5

In Preparation Example 1, except that the types and amounts of the colorant, block copolymer (B) and solvent were changed to those shown in Table 1, the same procedure was carried out as in Preparation Example 1 to prepare a colorant dispersion (A- 2) ~ (A-19).

<Evaluation of colorant dispersion>

The viscosity of the obtained colorant dispersion was measured with an E-type viscometer (manufactured by Tokyo Instruments). Moreover, the obtained colorant dispersion liquid was filled in the light-shielding glass container, and after leaving still at 23 degreeC in an airtight state for 14 days, the viscosity was measured again with the E-type viscometer (made by Tokyo Instruments). Then, the increase rate of the viscosity after 14-day storage with respect to the viscosity immediately after preparation was calculated, and the case where the increase rate was less than 5% was set as "A", and the case where the increase rate was 5% or more and less than 10% was set as "B". , The case of 10% or more was evaluated as "C". The evaluation results are shown in Table 2.

Table 2

In Table 2, "G58" means C.I. Pigment Green 58, "Y150" means C.I. Pigment Yellow 150, "B15:6" means C.I. Pigment Blue 15:6, "V23" means C.I. Pigment Violet 23, "Y179" means organic Dye C.I. Solvent Yellow 179, "PGMEA" means propylene glycol monomethyl ether acetate, "PGME" means propylene glycol monomethyl ether, and "BYK6919" means commercially available dispersant BYK-LPN6919 (manufactured by BYK Corporation). It should be noted that BYK-LPN6919 is a copolymer having a repeating unit (1) and a repeating unit (2) but not having a repeating unit with an acidic group, acid value = 0, amine value = 120 mgKOH/g (conversion of non-volatile components ), non-volatile component=60% by mass.

<Synthesis of binder resin>

Synthesis Example 13

In a flask equipped with cooling tube and stirrer, 44.0 g of p-vinylbenzyl glycidyl ether, 40.0 g of N-phenylmaleimide, 16.0 g of BzMA were dissolved in propylene glycol monomethyl ether acetate In 300 g, 8.0 g of AIBN and 8.0 g of α-methylstyrene dimer were further charged, and nitrogen purging was performed for 15 minutes. After nitrogen purging, the reaction solution was heated to 80° C. while stirring and blowing nitrogen gas to perform polymerization 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 the reaction solution, and reacted at 120° C. for 9 hours. Further, 18.5 g of succinic anhydride was added, and after reacting at 100° C. for 6 hours, the liquid temperature was maintained at 85° C., washed with water twice, and concentrated under reduced pressure to obtain a binder resin containing 33% by mass (D - a solution of 1). The weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) of the binder resin (D-1) = 7,800, the weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) Ratio to number average molecular weight = 2.8.

Synthesis Example 14

In a flask equipped with cooling tube and stirrer, 30.0 g of BzMA, 20.0 g of nBMA, 15.0 g of hydroxyethyl methacrylate, 20.0 g of styrene and 15.0 g of MA were dissolved in propylene glycol monomethyl ether acetic acid 3.0 g of AIBN and 5.0 g of α-methylstyrene dimer were further added to 200 g of the ester, and nitrogen purging was performed for 15 minutes. After the nitrogen purging, the reaction solution was heated to 80° C. and polymerized for 5 hours while stirring and blowing nitrogen gas to obtain a solution containing 33% by mass of the binder resin (D-2). The weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) of the binder resin (D-2) = 10,000, the weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) Ratio to number average molecular weight = 2.5.

Synthesis Example 15

In a flask equipped with a cooling tube and a stirrer, 25.0 g of 3-methylpropionyloxymethyl-3-ethyloxetane, 18.0 g of methacrylic acid, 9.0 g of succinic acid mono-2- Propionyloxyethyl ester, 10.0g of N-phenylmaleimide, 24.0g of BzMA, and 14.0g of hydroxyethyl methacrylate were dissolved in 300g of propylene glycol monomethyl ether acetate, and 6.0g was further added AIBN and 6.0 g of α-methylstyrene dimer, followed by a nitrogen purge for 15 min. After nitrogen purging, the reaction solution was heated to 80° C. for 5 hours while stirring and bubbling nitrogen gas, and polymerization was carried out to obtain a precursor copolymer solution.

13.4 g of 2-methacryloyloxyethyl isocyanate and 0.2 g of 4-methoxyphenol as a polymerization inhibitor were added to 200 g of the obtained precursor copolymer solution, and reacted at 90° C. for 2 hours. This reaction solution was washed twice with 75 g of ion-exchanged water each time, and concentrated under reduced pressure to obtain a solution containing 33% by mass of the binder resin (D-3). The weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) of the binder resin (D-3) = 11,000, the weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) Ratio to number average molecular weight = 1.9.

<Preparation and Evaluation of Coloring Composition>

Preparation of coloring composition

Example 1

100 parts by mass of colorant dispersion (A-1), 33.5 parts by mass of binder resin (D-2) as binder resin, 9.7 parts by mass of Toagosei Co., Ltd. M-402 (dipentaerythritol hexaacrylate is the main component), 4.3 parts by mass of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butane as a photopolymerization initiator- 1-ketone (trade name IRGACURE369, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 78.4 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed to prepare a liquid coloring composition.

Evaluation of clearing time

The obtained liquid composition was coated on a glass substrate by a spin coating method, and then prebaked for 2 minutes on a hot plate at 100° C. to form a coating film with a film thickness of 2.7 μm. Next, after cooling the substrate to room temperature, the coating film on the substrate was exposed to 1,000 J/m ² through a photomask using a high-pressure mercury lamp for each coating film with radiation of each wavelength including 365 nm, 405 nm, and 436 nm. Make an exposure. Then, shower image development was performed by spraying 23 degreeC 0.04 mass % potassium hydroxide aqueous solution to the coating film on a board|substrate. At this time, the time until the coating film of the unexposed portion was completely peeled off (cleaning time) was measured. And the case where the clearing time was less than 60 seconds was made "A", the case of 60 seconds or more and less than 120 seconds was made "B", and the case of 120 seconds or more was made "C", and evaluated. The shorter this time is, the faster the developing speed is, and there is an advantage that it is possible to shorten the lead time for color filter production. The evaluation results are shown in Table 3.

Evaluation of Chromaticity Characteristics

On the glass substrate, the obtained coloring composition was apply|coated by the spin coating method, and it prebaked for 2 minutes with the hot plate of 100 degreeC, and formed the coating film of 3 sheets from which film thickness differs. Next, after cooling the substrate to room temperature, the coating film on the substrate was exposed to 1,000 J/m ² of radiation including wavelengths of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp without passing through a photomask. amount of exposure. Then, post-baking was performed at 220° C. for 20 minutes to form a cured film on the substrate. For the obtained 3 cured films, use a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) to measure the chromaticity coordinate values (x, y) and stimulus values in the CIE colorimetric system with a C light source and a 2-degree field of view. (Y). From the measurement results, the chromaticity coordinate value x and the stimulus value (Y) at the chromaticity coordinate value y=0.590 were obtained. The evaluation results are shown in Table 3. For blue, find the Y value and x value when the y value is 0.090.

Embodiment 2～14 and comparative example 1～5

Except that in Example 1, the types and amounts of the colorant dispersion, binder resin, crosslinking agent, photopolymerization initiator, and solvent were changed to those shown in Table 3, the same procedure was carried out as in Example 1, whereby Preparation and evaluation of the coloring composition were performed. The evaluation results are shown in Table 3. In addition, regarding the cyan coloring composition (Example 6 and Comparative Example 3), the coordinate value x and the stimulus value (Y) of a color having a chromaticity coordinate value y=0.090 were obtained. The evaluation results are shown in Table 3.

table 3

In Table 3, each component is as follows.

C-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name M402, manufactured by Toagosei Co., Ltd.)

C-2: Dipentaerythritol pentaacrylate, a monoester compound of succinic acid, dipentaerythritol hexaacrylate, and a mixture of dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toagosei Co., Ltd.)

E-1: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) (trade name IRGACURE OX02, manufactured by Ciba Specialty Chemicals)

E-2: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (trade name IRGACURE369, manufactured by Ciba Specialty Chemicals)

EEP: ethyl 3-ethoxypropionate

MBA: 3-methoxybutyl acetate

Claims (17)

1. a color composition for color filter, is characterized in that, containing following composition (A), (B) and (C):

(A) colorant containing pigment;

(B) segmented copolymer, this segmented copolymer has the repetitive (1) shown in following formula (1), the repetitive (2) shown in following formula (2) and has the repetitive (3) of acidic-group, and the A block had containing described repetitive (1) and the B block containing described repetitive (2) and described repetitive (3), in described (B) segmented copolymer, the copolymerization ratios of the described repetitive (3) in whole repetitive is 0.5 ~ 15 quality %;

(C) crosslinking chemical;

In formula (1), R ¹represent hydrogen atom or methyl,

Z represents-N ⁺r ²r ³r ⁴y ^-,-NR ⁵r ⁶, maybe can have substituent nitrogen heterocycle, wherein, R ²~ R ⁴represent hydrogen atom independently of each other, maybe can have substituent alkyl, Y ^-represent counter anion, R ⁵and R ⁶represent hydrogen atom independently of each other, maybe can have substituent alkyl,

X ¹represent the linking group of divalent;

In formula (2), R ⁷represent that carbon number is the alkylidene of 2 ~ 4 independently of each other,

R ⁸represent that carbon number is the alkyl of 1 ~ 6,

R ⁹represent hydrogen atom or methyl,

N represents the integer of 1 ~ 150.

2. color composition for color filter according to claim 1, wherein, in described (B) segmented copolymer, the copolymerization ratios of the described repetitive (1) in whole repetitive is 5 ~ 70 quality %.

3. color composition for color filter according to claim 1, wherein, the weight-average molecular weight Mw of described (B) segmented copolymer is 1.0 ~ 1.8 with the ratio Mw/Mn of number-average molecular weight Mn.

4. color composition for color filter according to claim 1, wherein, further containing (D) resin glue, should not comprise described (B) composition by (D) resin glue.

5. color composition for color filter according to claim 1, wherein, further containing (E) Photoepolymerizationinitiater initiater.

6. color composition for color filter according to claim 1, wherein, contains dyestuff further as colorant.

7. color composition for color filter according to claim 1, wherein, in described (B) segmented copolymer, the copolymerization ratios of the described repetitive (3) in whole repetitive is 1 ~ 11 quality %.

8. color composition for color filter according to claim 1, wherein, in described (B) segmented copolymer, described B block has the repetitive (4) that following formula (4) represents, the copolymerization ratios of described repetitive (4), be 10 ~ 80 quality % in whole repetitive

In formula (4), R ¹⁸represent that hydrogen atom maybe can have substituent alkyl, R ¹⁹represent hydrogen atom or methyl.

9. color composition for color filter according to claim 1, wherein, in described (B) segmented copolymer, the copolymerization ratio of described A block and B block and the copolymerization ratio of A block/B block are 10/90 ~ 70/30 by quality ratio.

10. a color filter, is characterized in that, possesses and uses coloured composition according to any one of claim 1 ~ 9 and the dyed layer that formed.

11. 1 kinds of color liquid crystal display devices, is characterized in that, possess color filter according to claim 10.

12. 1 kinds of pigment dispersing liquid for colour filter, is characterized in that, containing following composition (A), (B) and (F):

(A) colorant containing pigment;

(B) segmented copolymer, this segmented copolymer has the repetitive (1) shown in following formula (1), the repetitive (2) shown in following formula (2) and has the repetitive (3) of acidic-group, and the A block had containing described repetitive (1) and the B block containing described repetitive (2) and described repetitive (3), in described (B) segmented copolymer, the copolymerization ratios of the described repetitive (3) in whole repetitive is 0.5 ~ 15 quality %;

(F) solvent;

In formula (1), R ¹represent hydrogen atom or methyl,

Z represents-N ⁺r ²r ³r ⁴y ^-,-NR ⁵r ⁶, maybe can have substituent nitrogen heterocycle, wherein, R ²~ R ⁴represent hydrogen atom independently of each other, maybe can have substituent alkyl, Y ^-represent counter anion, R ⁵and R ⁶represent hydrogen atom independently of each other, maybe can have substituent alkyl,

X ¹represent the linking group of divalent;

In formula (2), R ⁷represent that carbon number is the alkylidene of 2 ~ 4 independently of each other,

R ⁸represent that carbon number is the alkyl of 1 ~ 6,

R ⁹represent hydrogen atom or methyl,

N represents the integer of 1 ~ 150.

13. pigment dispersing liquid for colour filter according to claim 12, wherein, in described (B) segmented copolymer, the copolymerization ratios of the described repetitive (3) in whole repetitive is 1 ~ 11 quality %.

14. pigment dispersing liquid for colour filter according to claim 12, wherein, in described (B) segmented copolymer, described B block has the repetitive (4) that following formula (4) represents, the copolymerization ratios of described repetitive (4), be 10 ~ 80 quality % in whole repetitive

In formula (4), R ¹⁸represent that hydrogen atom maybe can have substituent alkyl, R ¹⁹represent hydrogen atom or methyl.

15. pigment dispersing liquid for colour filter according to claim 12, wherein, in described (B) segmented copolymer, the copolymerization ratio of described A block and B block and the copolymerization ratio of A block/B block are 10/90 ~ 70/30 by quality ratio.

16. pigment dispersing liquid for colour filter according to claim 12, wherein, described (F) solvent contains (f1) and has the solvent that the solvent of hydroxyl and (f2) do not have hydroxyl.

17. pigment dispersing liquid for colour filter according to claim 16, wherein, what described (f1) in described (F) solvent had that the solvent of hydroxyl and described (f2) do not have the solvent of hydroxyl is 0.5/99.5 ~ 40/60 containing mass ratio.