KR101982882B1 - Coloring composition for color filter, color filter and display device - Google Patents

Abstract

[화학식 (1)에 있어서, R¹은 수소 원자 또는 메틸기를 나타내고, Z는 -NR²R³(단, R² 및 R³은 서로 독립적으로 수소 원자, 또는 치환 또는 비치환의 탄화수소기를 나타냄), 또는 치환 또는 비치환의 질소 함유 복소환기를 나타내고, X¹은 2가의 연결기를 나타내고,
화학식 (2)에 있어서, R⁴는 수소 원자 또는 메틸기를 나타내고, R⁵는 지방족 탄화수소기 또는 지환식 탄화수소기를 나타냄]Disclosure of the Invention An object of the present invention is to provide a coloring composition for a color filter excellent in chromaticity characteristics, good in dispersibility and storage stability.
The inventive solution comprises the following components (A), (B) and (C);
(A) a colorant comprising a quinophthalone-based pigment,
(B) a copolymer comprising a repeating unit (1) represented by the following formula (1) and a repeating unit (2) represented by the following formula (2) and having an amine value of 80 to 250 mgKOH / g, and
(C) a crosslinking agent.

Wherein R ¹ represents a hydrogen atom or a methyl group, Z represents -NR ² R ³ (provided that R ² and R ³ independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group), Or a substituted or unsubstituted nitrogen-containing heterocyclic group, X ¹ represents a divalent linking group,
In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

Description

TECHNICAL FIELD [0001] The present invention relates to a coloring composition, a color filter, and a display device for a color filter,

The present invention relates to a coloring composition for a color filter, a color filter and a display device, and more particularly to a color filter for a color filter used for a transmissive or reflective color liquid crystal display device, a solid-state image sensor, an organic EL display device, A color filter comprising a coloring layer formed using the coloring composition, and a display device including the color filter.

In the production of a color filter using a coloring and radiation-sensitive composition, a coloring and radiation-sensitive composition of a pigment dispersion type is coated on a substrate and dried, and then the dry film is irradiated with a desired pattern (hereinafter referred to as "exposure" (For example, Patent Documents 1 and 2) are known. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (for example, Patent Document 3) is also known. There is also known a method (for example, Patent Document 4) of obtaining a pixel of each color by an ink jet method using a pigment dispersion type colored resin composition.

However, in the field of color filters used for liquid crystal display elements and solid-state image pickup elements, the pigments used tend to become more and more atomized in response to demands for higher brightness and higher contrast. It is known that it is effective to use a dispersant in order to realize stable and good dispersion of such an atomized pigment. There have been proposed various methods (for example, Patent Documents 5 to 6) for improving the dispersibility of the pigment using such a dispersant and improving not only contrast and dispersion stability but also developability and the like.

Japanese Patent Application Laid-Open No. 2-144502 Japanese Patent Laid-Open Publication No. 3-53201 Japanese Patent Application Laid-Open No. 6-35188 Japanese Patent Application Laid-Open No. 2000-310706 Japanese Patent Application Laid-Open No. 2003-26949 Japanese Patent Application Laid-Open No. 2009-25813

However, even with the methods described in Patent Documents 5 to 6, it is difficult to realize the recent requirement of high contrast, high color purity and high brightness of a color liquid crystal display device. Particularly in the case of using a quinophthalone-based pigment represented by CI Pigment Yellow 138 as a coloring agent, the conventionally proposed dispersion method and the pigment dispersion solution produced by a known dispersing agent not only have high viscosity but also poor storage stability It is difficult to withstand practical use. Further, the color filter produced by using the pigment dispersion solution has a problem that the contrast is insufficient. Therefore, there is a strong demand for the development of a coloring composition for a color filter which realizes a recent demand for high contrast, high color purity and high brightness, and which is excellent in dispersibility and storage stability.

Accordingly, an object of the present invention is to provide a coloring composition for a color filter which is excellent in chromaticity characteristics and excellent in dispersibility and storage stability by using a quinophthalone-based pigment represented by CI Pigment Yellow 138 as a coloring agent. Another object of the present invention is to provide a color filter comprising a colored layer formed of the colored composition, and a display device having the color filter.

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

That is, the present invention relates to the following components (A), (B) and (C);

(A) a colorant comprising a quinophthalone-based pigment,

(B) a repeating unit represented by the following formula (1) (hereinafter also referred to as a "repeating unit (1)") and a repeating unit represented by the following formula (2) (Hereinafter also referred to as " (B) copolymer ") having an amine value of 80 to 250 mgKOH / g, and

(C) Crosslinking agent

And a coloring composition for a color filter.

[In the formula (1)

R ¹ represents a hydrogen atom or a methyl group,

Z represents -NR ² R ³ (wherein R ² and R ³ independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group) or a substituted or unsubstituted nitrogen-containing heterocyclic group,

X < ¹ > represents a divalent linking group]

[In the formula (2)

R ⁴ represents a hydrogen atom or a methyl group,

R < ⁵ > represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

Further, the present invention provides a color filter comprising a colored layer formed using the coloring composition, and a display element comprising the color filter. Here, the " colored layer " means each color pixel, a black matrix, a black spacer, and the like used in the color filter.

The present invention also relates to the following components (a1), (B) and (F);

(a1) a quinophthalone-based pigment,

(B) a copolymer containing a repeating unit (1) and a repeating unit (2) and having an amine value of 80 to 250 mgKOH / g, and

(F) Solvent

To provide a pigment dispersion for a color filter.

The coloring composition for a color filter of the present invention is excellent in chromaticity characteristics and excellent in dispersibility and storage stability. By using the coloring composition of the present invention, a color filter having each color pixel with high contrast can be obtained.

Therefore, the coloring composition for a color filter of the present invention is useful for the production of various color filters including a color filter for a color liquid crystal display element, a color filter for color separation of a solid-state image pickup element, a color filter for an organic EL display element, And can be used very preferably.

Hereinafter, the present invention will be described in detail.

Coloring composition for color filter

Hereinafter, the constituent components of the coloring composition for a color filter of the present invention (hereinafter, simply referred to as " coloring composition ") will be described.

- (A) Colorant -

The coloring composition of the present invention is characterized by comprising (A) a quinophthalone-based pigment (a1) as a colorant.

As the quinophthalone-based pigment, CI Pigment Yellow 138 is preferable from the viewpoints of availability of raw materials and absorption spectrum.

In the present invention, (a1) quinophthalone pigments may be used singly or in combination of two or more kinds. In addition, the coloring composition of the present invention may further contain (a2) another colorant together with (a1) quinophthalone-based pigment as a colorant. (a2) Other colorants are not particularly limited, and for example, (a1) quinophthalone pigments may be used together with a green colorant to form a coloring composition for forming green pixels. Further, by using (a1) a quinophthalone-based pigment together with a red coloring agent, a colored composition for forming a red pixel or a yellow pixel can be obtained.

(a2) As the other colorants, any of pigments, dyes and natural pigments other than quinophthalone pigments can be used, but organic pigments and organic dyes are preferred in the sense of obtaining pixels with high brightness and color purity. Examples of organic pigments include compounds classified by pigment in the color index (published by CI Society of Dyers and Colourists), that is, color index (C.I.) names as shown below.

CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, CI Pigment Yellow 211;

CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 46, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, 72, CI Pigment Orange 73, CI Pigment Orange 74;

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

CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38;

CI Pigment Blue 1, CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60, CI Pigment Blue 80;

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

CI Pigment Brown 23, CI Pigment Brown 25;

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

The xanthan-based lake pigment described in JP-A-2010-26334;

Rhodamine lake pigments described in JP-A-2010-191304 and JP-A-2011-22502;

Triarylmethane lake pigments described in Japanese Patent Laid-Open Publication No. 2011-138094 and Japanese Patent Laid-Open No. 2011-22502;

Various rake pigments described in JP-A-2010-237569, JP-A-2011-6602, and JP-A-2011-150195.

Examples of the organic dyes include those having a color index (C.I.) name as shown below.

CI Acid Blue 28, CI Direct Blue 28, CI Direct Yellow 28, CI Direct Yellow 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7;

Anthraquinone dyes such as CI Bat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60 ;

Phthalocyanine dyes such as C. I. Bat Blue 5;

Quinone imine dyes such as C.I. Basic Blue 3 and C.I. Basic Blue 9;

Quinoline dyes such as C.I. Solvent Yellow 33, C.I. Acid Yellow 3 and C.I. Disperse Yellow 64;

Nitro-based dyes such as C.I. Acid Yellow 1, C.I. Acid Orange 3, and C.I. Disperse Yellow 42;

Disperse Yellow 201 and the like.

In the present invention, (a2) other colorants may be used alone or in combination of two or more.

In the present invention, the pigment may be purified and used by recrystallization, reprecipitation, solvent cleaning, sublimation, vacuum heating, or a combination thereof. The pigment may be used by modifying the surface of the particles with a resin according to purposes. As the resin for modifying the particle surface of the pigment, for example, a vehicle resin disclosed in Japanese Patent Application Laid-Open No. 2001-108817 or a resin for dispersing various pigments on the market can be mentioned. Examples of the resin coating method for the carbon black surface include a method described in Japanese Patent Application Laid-Open No. 9-71733, Japanese Patent Application Laid-Open No. 9-95625, Japanese Patent Application Laid-Open No. 9-124969 Can be adopted. The organic pigment may be used by finely pulverizing primary particles by so-called salt milling. As a method of the salt milling, for example, a method disclosed in Japanese Unexamined Patent Application Publication No. 08-179111 can be adopted.

When the coloring composition of the present invention is used for the formation of a green pixel, (A) a colorant is preferably used in combination with a quinophthalone-based pigment (a1), a group consisting of CI Pigment Green 7, CI Pigment Green 36 and CI Pigment Green 58 At least one kind selected from the group consisting of In this case, the content of the quinophthalone-based pigment (a1) is preferably 1 to 80% by mass, more preferably 2 to 70% by mass in the total colorant, and the content of the CI Pigment Green 7, the CI Pigment Green 36, CI Pigment Green 58 is preferably 20 to 99% by mass, more preferably 30 to 98% by mass in the total colorant.

The content ratio of the (A) coloring agent is usually from 5 to 70% by mass, preferably from 5 to 60% by mass in the solid content of the coloring composition in view of forming a pixel having a high luminance and excellent color purity or a black matrix having excellent light- %to be. Here, the solid content is a component other than the solvent described later.

- (B) Copolymer -

The copolymer (B) in the present invention is a copolymer containing the repeating unit (1) and the repeating unit (2) and having an amine value of 80 to 250 mgKOH / g, and functions as a dispersant of the (A) colorant.

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

In the above formula (1), R ¹ is preferably a hydrogen atom or a methyl group in the methyl group.

In the above formula (1), Z represents -NR ² R ³ or a substituted or unsubstituted nitrogen-containing heterocyclic group, R ² and R ³ independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, The term " hydrocarbon group " in the present invention is a concept including an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and may be any of linear, branched and cyclic forms, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group . The position of the unsaturated bond of the unsaturated hydrocarbon group may be either in the molecular chain or at the molecular chain terminal.

The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, more specifically an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, An alkynyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, , An octyl group, a decyl group, and a dodecyl group. Examples of the alkenyl group include an ethynyl group, an 1-propenyl group, a 1-butenyl group, a 1,3-butadienyl group, Pentenyl group, 2-butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group and 2-decenyl group. Examples of the alkynyl group include an ethynyl group, -Butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, 2-octynyl group, .

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and specifically, a cycloalkyl group having 3 to 20 carbon atoms and further 3 to 12 carbon atoms can be exemplified. More specifically, A propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group. Herein, in the present invention, the "alicyclic hydrocarbon group" is a generic term of a carbon-cyclic compound having a structure in which carbon atoms are bonded in a cyclic structure except for an aromatic compound, and includes the above-mentioned aliphatic hydrocarbon group as a substituent or a linking group with -COO- .

The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably 6 to 14, further preferably 6 to 10 carbon atoms, and more specifically, an aryl group having 6 to 20 carbon atoms, more preferably 6 to 14, . Here, in the present invention, the "aryl group" refers to a monocyclic to tricyclic aromatic hydrocarbon group, and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and an azulenyl group.

Examples of the substituent of the hydrocarbon group include a halogen atom, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, Pentyl group, phenoxy group and the like.

In the present invention, the "nitrogen-containing heterocyclic group" refers to a heterocyclic group having at least one nitrogen atom as a constituent of the ring, and is preferably a heterocyclic group or a condensed heterocyclic group formed by condensing two of them. These heterocyclic groups may be an unsaturated ring or a saturated ring, and may have a hetero atom (e.g., oxygen atom, sulfur atom) other than a nitrogen atom in the ring.

Examples of the unsaturated heterocycle include a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a triazole ring, an imidazoline ring, and a piperazine ring. Examples of the saturated heterocycle include a morpholine ring, piperidine ring, and tetrahydropyrimidine ring. Examples of the substituent in the nitrogen-containing heterocyclic group include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a carboxyl group, an alkoxycarbonyl group, an alkoxy group, a hydroxyl group, an amino group, an amide group, a thiol group and a thioether group . Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group and a hexyl group. Examples of the halogen atom include a fluorine atom, Bromine atom, and iodine atom. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 7 carbon atoms, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a formyloxy group, an acetoxy group, and a benzoyloxy group. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, and specific examples thereof include a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group and phenoxy group. Examples of the amino group include an amino group, a methylamino group, a diethylamino group and a diphenylamino group. Examples of the amide group include a formamide group, an acetamide group and a propioamide group. The thioether group is preferably a thioether group having 1 to 6 carbon atoms, and specific examples thereof include a methylthioether group, an ethylthioether group and a butylthioether group.

The above-mentioned heterocyclic group is preferably a 5- to 7-membered ring, specifically, a group having a basic skeleton represented by the following formula (1-1), and these heterocyclic groups may have a substituent.

In the formula (1-1), " * " represents a bonding hand.

Specific examples of the condensed heterocyclic group include groups having a basic skeleton represented by the following formulas (1-2) to (1-4), and these condensed heterocyclic groups may have a substituent.

In the formulas (1-2) to (1-4), " * "

In the above formula (1), examples of the divalent linking group (X ¹ ) include an alkanediyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms; An arylene group having 6 to 20, more preferably 6 to 14 carbon atoms; -CONH-R < ¹⁰ > - group; -COO-R < ¹¹ > - group and the like. Here, R ¹⁰ and R ¹¹ are independently of each other a single bond, an alkanediyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, or an alkyleneoxyalkylene group having 2 to 10 carbon atoms. Examples of the alkanediyl group include a methylene group, an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, 1,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane- -Diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group and the like. Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group. Examples of the alkyleneoxyalkylene group having 2 to 10 carbon atoms include an ethyleneoxyethylene group, an ethyleneoxypropylene group, a propyleneoxypropylene group and an ethyleneoxybutylene group.

Among them, X ¹ is preferably -COO-R ¹¹ - group, and R ¹¹ is preferably an alkanediyl group having 2 to 6 carbon atoms.

The repeating unit (2) is represented by the above formula (2).

In the above formula (2), R ⁴ is preferably a hydrogen atom or a methyl group in the methyl group.

Examples of the aliphatic hydrocarbon group for R ⁵ include an alkyl group, an alkenyl group and an alkynyl group. The aliphatic hydrocarbon group may be any of linear and branched forms, and when the aliphatic hydrocarbon group is an alkenyl group or an alkynyl group, the position of the unsaturated bond may be either in the molecular chain or at the molecular chain terminal.

Examples of the alicyclic hydrocarbon group for R ⁵ include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a crosslinked ring hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene hydrocarbon group. The alicyclic hydrocarbon group may further have a substituent. Examples of such a substituent include a halogen atom, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms. Specific examples of these substituents include those described above.

Among them, R ⁵ is preferably an alkyl group having 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms and more preferably 4 to 15 carbon atoms. Specific examples thereof include a methyl group, ethyl group, propyl group, butyl group, , t-butyl group, 2-ethylhexyl group, isodecyl group, dodecyl group, cyclohexyl group, t-butylcyclohexyl group, decahydro-2-naphthyl group, tricyclo [5.2.1.0 ^2,6 ] An 8-yl group, an adamantyl group, a dicyclopentenyl group, a pentacyclopentadecanyl group, a tricyclopentenyl group and an isobornyl group are particularly preferable.

The copolymer (B) may have a repeating unit other than the above. Examples of such repeating units include repeating units represented by the following formula (3) [hereinafter also referred to as "repeating units (3)"); A repeating unit having an acidic group (hereinafter also referred to as "repeating unit (4)"); Styrene-based monomers such as styrene and? -Methylstyrene; (Meth) acrylic acid aralkyl esters such as benzyl (meth) acrylate; A quaternary ammonium salt structure such as (meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium chloride and (meth) acryloyloxyethylbenzyldiethylammonium chloride (Meth) acrylic acid esters having (meth) acrylic acid esters; (Meth) acrylic acid halide monomers such as (meth) acrylic acid chloride; (Meth) acrylamide, N-methylol acrylamide, and other (meth) acrylamide monomers; Vinyl acetate; Acrylonitrile; Allyl glycidyl ether; Crotonic acid glycidyl ether; And repeating units derived from a monomer such as N-methacryloylmorpholine. Among them, it is preferable to have at least one of the repeating unit (3) and the repeating unit (4) from the viewpoint of dispersibility, and it is more preferable to have the repeating unit (3). Here, in the present invention, "(meth) acrylate" means "acrylate or methacrylate".

[In the formula (3)

R ⁶ represents a hydrogen atom or a methyl group,

R ⁷ independently represents an alkanediyl group having 2 to 4 carbon atoms,

R ⁸ represents an alkyl group having 1 to 6 carbon atoms,

and n represents an integer of 1 to 150)

In the formula (3), R ⁶ is preferably a hydrogen atom or a methyl group in the methyl group.

Examples of the alkanediyl group for R ⁷ include an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, Diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group and the like.

Examples of the alkyl group for R ⁸ include the same ones as described above.

n represents an integer of 1 to 150, but is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

The repeating unit (4) is gatneunde an acidic group, such as the acidic group is not particularly limited, for example, include a phenolic hydroxyl group, a carboxyl group, a sulfo _{group, -SO 2 NH 2, -C (} CF 3) 2 -OH , etc. . In the present invention, as the acidic group, a phenolic hydroxyl group and a carboxyl group are preferable from the viewpoints of dispersibility and alkali developability of the resulting colored composition, and a carboxyl group is particularly preferable.

The repeating unit (4) includes, for example, a repeating unit represented by the following formula (4).

[In the formula (4)

R ⁹ represents a hydrogen atom or a methyl group,

A represents an acidic group,

X < ^{2 >} represents a single bond or a divalent linking group]

In the above formula (4), R ⁹ is preferably a hydrogen atom or a methyl group in the methyl group.

Examples of the divalent linking group (X ² ) include an alkanediyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, an arylene group, a -CONH-R ¹² group, a -COO-R ¹³ group, a -OCOR ¹⁴ group , -R ¹⁵ -OCO-R ¹⁶ -, -COO- (C _m H _2m COO) ₁ -C _m H _2m - group, -COO-R ¹⁷ -OCO-R ¹⁸ - and the like. R ¹² to R ¹⁶ independently represent a single bond, an alkylidene group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, or an alkyleneoxyalkylene group having 2 to 10 carbon atoms, and m is an integer of 1 to 10, R ¹⁷ represents an alkanediyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms; R ¹⁸ represents a single bond, an alkanediyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, , A cyclohexane-1,2-diyl group or a phenylene group (for example, a 1,2-phenylene group or a 1,4-phenylene group). Specific examples of the alkanediyl group, arylene group and alkyleneoxyalkylene group are the same as those described above.

Among them, X ^{2 is preferably a} single bond, a phenylene group, a -COO-R ¹³ group, a -COO- (C _m H _2m COO) _l C _m H _2m group or a -COO-R ¹⁷ -OCO-R ¹⁸ - desirable.

In the copolymer (B), the copolymerization ratio of each repeating unit is not particularly limited as long as the amine value of the copolymer is in the range of 80 to 250 mgKOH / g, but from the viewpoint of dispersibility, (i) to (iii) ), And more preferably any one of (ii) and (iii).

(i) When the copolymer (B) comprises only the repeating unit (1) and the repeating unit (2), the copolymerization ratio of the repeating unit (1) is preferably 20 to 80 mass% 30 to 70% by mass, more preferably 40 to 60% by mass, and the copolymerization ratio of the repeating unit (2) is the remainder.

(ii) When the copolymer (B) has a repeating unit (3) other than the repeating unit (1) and the repeating unit (2), the copolymerization ratio of the repeating unit (1) , More preferably 30 to 65 mass%, and still more preferably 40 to 60 mass%, and the copolymerization ratio of the repeating unit (2) is preferably 5 to 50 mass%, more preferably 5 to 50 mass% Is 10 to 45% by mass, more preferably 15 to 40% by mass, and the copolymerization ratio of the repeating unit (3) is preferably 5 to 40% by mass, more preferably 10 to 30% by mass.

(iii) When the copolymer (B) has the repeating unit (3) and the repeating unit (4) other than the repeating unit (1) and the repeating unit (2), the copolymerization ratio of the repeating unit The copolymerization ratio of the repeating unit (2) is preferably 5 to 50% by mass, more preferably 20 to 70% by mass, further preferably 30 to 65% by mass, further preferably 40 to 60% Is 10 to 45% by mass, more preferably 15 to 40% by mass, and the copolymerization ratio of the repeating unit (3) is preferably 5 to 40% by mass, more preferably 10 to 30% The copolymerization ratio of the repeating unit (4) is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, in the total repeating units.

The amine value of the copolymer (B) is not less than 80 mgKOH / g but not more than 250 mgKOH / g, but from the viewpoint of further improvement of the contrast, preferably from 100 to 250 mgKOH / g, more preferably from 150 to 250 mgKOH / g, 200 mgKOH / g, particularly preferably 155 to 190 mgKOH / g. Here, in the present invention, "amine value" means the number of mg of KOH equivalent to the acid necessary to neutralize 1 g of the non-volatile matter from which the solvent of the copolymer solution has been removed, specifically, the value measured by the method described in the following Examples It says.

On the other hand, when the copolymer (B) has the repeating unit (4), the acid value of the copolymer (B) is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, Is not more than 20 mg KOH / g. The lower limit is not particularly limited, but is preferably 0.5 mgKOH / g or more, more preferably 1 mgKOH / g or more. Here, in the present invention, the "acid value" means the number of mg of KOH required to neutralize 1 g of the nonvolatile matter from which the solvent of the copolymer solution has been removed, specifically the one measured by the method described in the following examples.

The repeating unit (2), the repeating unit (3) and the repeating unit (4) are not particularly limited as long as they have the repeating unit (1) and the repeating unit (2) (2), a repeating unit (3), and a B block having a repeating unit (4) in accordance with the purpose, without repeating unit (1) Is preferably a block copolymer. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer.

In the A block, the repeating unit (1) may contain two or more kinds of repeating units (A) in one A block. In this case, the repeating units may be contained in the A block in any of random copolymerization and block copolymerization .

The repeating units other than the repeating unit (1) may be contained in the A block. Examples of such repeating units include repeating units derived from the (meth) acrylic acid ester having the above quaternary ammonium salt structure.

On the other hand, in the B block, the repeating unit (2), the repeating unit (3) and the repeating unit (4) may be contained in any of random copolymerization and block copolymerization. When the (B) copolymer is a BAB block copolymer, the B1 block having the repeating unit (2) and the repeating unit (3) but not having the repeating unit (4) Or a B1-A-B2 block copolymer having a B2 block having no repeating unit (3). The repeating unit (2), the repeating unit (3) and the repeating unit (4) may contain two or more kinds of repeating units in each of the B blocks. In this case, And block copolymerization.

The copolymer (B) can be produced by a known method. When the copolymer (B) is a block copolymer, it can be prepared, for example, by living polymerization of a monomer introducing each repeating unit. As the living polymerization method, for example, JP-A-9-62002; Japanese Patent Laid-Open No. 2002-31713; See P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984); B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985); K. Hatada, K. Ute, et al, Polym. J.18, 1037 (1986); 36, 366 (1987)); < RTI ID = 0.0 > (Higashimura City Nobu, Sawamoto Mitsuo, Polymer Journal, 46, 189 (1989)); M. Kuroki, T. Aida, J. Am. Chem. Soc., 109, 4737 (1987); AIDA Takako, Inoue Shohei, Organic Synthesis Chemistry, 43, 300 (1985)]; D. Y.Sogoh, W. R. Hertler 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)).

Examples of the monomer which provides the repeating unit (1) include monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl And the like. These may be used alone or in combination of two or more.

Examples of the monomer providing the repeating unit (2) include monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isopropyl (meth) acrylate, , tricyclo [5.2.1.0 ^2,6] decane-8-yl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Decahydro-2-naphthyl (meth) acrylate, pentacyclopentadecanyl (meth) acrylate, and tricyclopentenyl (meth) acrylate. These may be used alone or in combination of two or more.

Examples of the monomer providing the repeating unit (3) include monomers such as 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxypropylene glycol (Meth) acrylate, methoxydipropylene glycol (meth) acrylate, and the like. These may be used alone or in combination of two or more.

Examples of the monomer providing the repeating unit (4) include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, (meth) acrylic acid carboxymethyl ester, (meth) (Meth) acryloyloxyethyl], [omega] -carboxypolycaprolactone mono (meth) acrylate, p-vinylbenzoic acid, p- hydroxystyrene, p- Acryloyloxyethylsulfonic acid, methylstyrene, 2-acryloyloxyethylsulfonic acid, 2-methacryloxyethylsulfonic acid, sodium 2-acryloyloxyethylsulfonate, lithium 2-acryloyloxyethylsulfonate, Acryloyloxyethylsulfonic acid imidazolium, 2-acryloyloxyethylsulfonylpyridinium, 2-methacryloxyethylsulfonic acid sodium, 2-methacryloxyethylsulfonic acid lithium, 2-methacryloxyethylsulfonic acid ammonium, Imidazolium 2-methacryloxyethylsulfonate, 2- Pyridinium methacrylate, pyridinium methacrylate, pyridinium methacrylate, pyridinium methacrylate, These may be used alone or in combination of two or more.

The molecular weight of the (B) copolymer is preferably 1,000 to 30,000, particularly preferably 5,000 to 15,000 in terms of Mw in terms of methyl polymethacrylate measured by GPC (elution solvent: DMF).

The ratio (Mw / Mn) of the Mw of the block copolymer (B) to the Mn as reduced to polymethyl methacrylate measured by GPC (dissolution solvent: DMF) is preferably 1.0 to 1.9, more preferably 1.0 To 1.8, more preferably 1.0 to 1.7, more preferably 1.0 to 1.5, and particularly preferably 1.0 to 1.3. (B) copolymer in this embodiment, a colored composition excellent in dispersibility and alkali developability can be obtained.

(B) may be used alone or in combination of two or more. The content of the copolymer (B) is usually 1 to 100 parts by mass, preferably 5 to 70 parts by mass, and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the (A) colorant. If the content of the (B) copolymer is too large, there is a fear that the developability is deteriorated.

In the present invention, a known dispersant may be further contained in order to improve the dispersibility. Examples of the known dispersant include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkyl phenyl ether-based dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester- Dispersants, acrylic dispersants, pigment derivatives, and the like.

Dispersing agents such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 and BYK-LPN21324 (manufactured by BYK), as urethane dispersants, are commercially available as commercially available products, Dispersing agents such as Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170 and Disperbyk-182 (manufactured by Bikkimisakusha), Solpus 76500 (manufactured by Lubrizol) (Manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like can be mentioned as the dispersant of the present invention. Examples of the dispersant include Agisper PB821, Ajisper PB822, Ajisper PB880 and Ajisper PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.). Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

- (C) Crosslinking agent -

In the present invention, (C) a crosslinking agent means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenic unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, as the (C) crosslinking agent, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, a polyfunctional (meth) acrylate modified with caprolactone , A polyfunctional urethane (meth) acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, a (meth) acrylate having a hydroxyl group and an acid anhydride (Meth) acrylate having a carboxyl group which is obtained by reacting a polyfunctional (meth) acrylate.

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, glycerin, trimethylol propane, pentaerythritol, dipentaerythritol, And an aliphatic polyhydroxy compound having the same trivalent or more. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, and glycerol dimethacrylate. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, anhydrous glutaric acid, itaconic anhydride, phthalic anhydride and hexahydrophthalic anhydride, anhydrous pyromellitic acid, biphenyltetracarboxylic acid dianhydride , And benzophenone tetracarboxylic acid dianhydride.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of Japanese Patent Laid-Open No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include di (meth) acrylate modified with at least one selected from ethylene oxide of bisphenol A and propylene oxide of bisphenol A, ethylene oxide of isocyanuric acid (Meth) acrylate modified with at least one member selected from the group consisting of isophorone diisocyanate, isophorone diisocyanate, and isocyanuric acid propylene oxide, trimethylolpropane ethylene oxide and trimethylolpropane propylene oxide. Tri (meth) acrylate modified with at least one member selected from ethylene oxide of pentaerythritol, propylene oxide of pentaerythritol, ethylene oxide of pentaerythritol, and propylene oxide of pentaerythritol Lt; RTI ID = 0.0 > (Meth) acrylate modified with at least one member selected from tetra (meth) acrylate, ethylene oxide of dipentaerythritol and propylene oxide of dipentaerythritol, ethylene oxide of dipentaerythritol and dipentaerythritol And hexa (meth) acrylate modified by at least one kind selected from propylene oxide of lithol and the like.

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. Further, the melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as basic skeletons, and also include melamine, benzoguanamine, or condensates thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N '', N '' - hexa (alkoxymethyl) melamine, N, N ' (Alkoxymethyl) benzoguanamine, N, N, N ', N'-tetra (alkoxymethyl) glycoluril and the like.

(Meth) acrylate, caprolactone-modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate and carboxyl group obtained by reacting a tri- or higher valent aliphatic polyhydroxy compound with (meth) N, N ', N', N'-tetra (alkoxymethyl) melamine, N, N ' Benzoguanamine is preferred. Among the multifunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, Among the polyfunctional (meth) acrylates having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride, From the viewpoint that the strength of the colored layer is high and the surface smoothness of the colored layer is excellent and background contamination and film residue are hardly formed on the substrate of the unexposed portion and on the light shielding layer.

In the present invention, the crosslinking agent (C) may be used alone or in combination of two or more.

The content of the crosslinking agent (C) in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. In this case, if the content of the cross-linking agent is too small, there is a possibility that sufficient curability is not obtained. On the other hand, when the content of the crosslinking agent is too large, alkali developing property is lowered when the alkali developing property is imparted to the coloring composition of the present invention, and background contamination, film residue or the like easily occurs on the substrate of the unexposed portion or on the light- There is a tendency to lose.

- (D) Binder Resin -

The coloring composition of the present invention may contain (D) a binder resin (excluding the above component (B)). This makes it possible to improve the alkali developing property and the binding property to the substrate to the coloring composition. Such a binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. (Hereinafter referred to as " carboxyl group-containing polymer ") is preferable, and an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter referred to as " unsaturated monomer (d1) (Hereinafter referred to as " unsaturated monomer (d2) ").

Examples of the unsaturated monomer (d1) include mono [2- (meth) acryloyloxyethyl], [omega] -carboxypolycaprolactone mono (meth) acrylate such as (meth) acrylic acid, maleic acid, maleic anhydride, , p-vinylbenzoic acid, and the like.

These unsaturated monomers (d1) may be used alone or in admixture of two or more.

As the unsaturated monomer (d2), for example,

N-substituted maleimide such as N-phenylmaleimide, N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene,? -Methylstyrene, p-hydroxystyrene, p-hydroxy-? -Methylstyrene, p-vinylbenzyl glycidyl ether and acenaphthylene;

Acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) (Meth) acrylate, polyethylene glycol (having a degree of polymerization of 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (having a degree of polymerization of 2 to 10) (Meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, propylene glycol (Meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide- ) Acrylate, 3,4- Acrylate such as (meth) acryloyloxymethyl] -3-ethyloxetane, 3 - [(meth) acryloyloxymethyl] oxetane, 3 - [(meth) acryloyloxymethyl] ;

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

And a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.

These unsaturated monomers (d2) may be used alone or in admixture of two or more.

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

As specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2), for example, JP-A-7-140654, JP-A-8-259876, Japanese Patent Laid-Open Nos. 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118 And Japanese Patent Application Laid-Open No. 2004-101728.

Further, in the present invention, for example, Japanese Patent Application Laid-Open No. 5-19467, Japanese Patent Application Laid-Open No. 6-230212, Japanese Patent Application Laid-Open No. 7-207211, (Meth) acryloyl groups such as (meth) acryloyl groups on the side chains as disclosed in Japanese Patent Application Laid-Open Nos. 09-325494, 11-140144 and 2008-181095, May be used as the binder resin.

The binder resin in the present invention has a weight average molecular weight of 1,000 to 100,000, preferably 3,000 to 50,000 in terms of polystyrene measured by GPC (dissolution solvent: tetrahydrofuran). If the Mw is too small, there is a risk that the residual film ratio or the like of the resulting film deteriorates, the pattern shape, the heat resistance, and the like are deteriorated and the electrical characteristics deteriorate. On the other hand, In addition, there is a concern that dry foreign matter tends to be generated when applying by the slit nozzle method.

The ratio (Mw '/ Mn') of the weight average molecular weight (Mw ') to the number average molecular weight (Mw') of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. Herein, Mw 'and Mn' refer to weight average molecular weight and number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

The binder resin in the present invention can be prepared by a known method, for example, Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871 , The structure or Mw and Mw / Mn can be controlled

In the present invention, the binder resins may be used alone or in combination of two or more.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. If the content of the binder resin is too small, for example, the alkaline developability may deteriorate or the storage stability of the resulting colored composition may deteriorate. On the other hand, when the content is too large, the colorant concentration is relatively lowered. It may be difficult to achieve the color density.

- (E) Photopolymerization initiator -

(E) a photopolymerization initiator may be contained in the coloring composition of the present invention. Thereby, the coloring composition can be imparted with radiation sensitivity. The (E) photopolymerization initiator used in the present invention is a compound which generates an active species capable of initiating polymerization of the crosslinking agent (C) by exposure to radiation such as visible light, ultraviolet light, deep ultraviolet light, electron beam or X-ray.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, nonimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, -Diketone-based compounds, polynuclear quinone-based compounds, diazo-based compounds, and imidosulfonate-based compounds.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. As the photopolymerization initiator, at least one member selected from the group consisting of a thioxanone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, and an O-acyloxime compound is preferable.

Specific examples of the thioxanone compound in the photopolymerization initiator of the present invention include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone.

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

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 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 and the like.

When a nonimidazole-based compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination because it can improve the sensitivity. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a nonimidazole-based compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis Ethylamino) benzophenone, and the like. In the present invention, the hydrogen donors may be used singly or in combination of two or more. However, the combination of at least one mercaptan-based hydrogen donor and at least one amine-based hydrogen donor makes it possible to further improve the sensitivity .

Specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) 2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan- Bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] 2- (4-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4 , 6-bis (trichloromethyl) -s-triazine, and other triazine compounds having a halomethyl group.

Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O- benzoyloxime), ethanone, 1- [ (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime), ethanone, 1- [ Yl) -, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- { Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -, 1- (O-acetyloxime). As commercial products of O-acyloxime compounds, NCI-831 and NCI-930 (manufactured by ADEKA) can be used.

In the present invention, when a photopolymerization initiator other than a non-imidazole-based compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. Examples of such sensitizers include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone , Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino- ) Coumarin, and 4- (diethylamino) chalcone.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, the curing by exposure may become insufficient, while if it is excessively large, the formed colored layer tends to fall off from the substrate at the time of development.

- (F) Solvent-

The coloring composition of the present invention can be obtained by mixing a colorant containing (a1) a quinophthalone-based pigment in (F) a solvent, (B) a copolymer and optionally another dispersing agent or (D) (C) a crosslinking agent, (D) a binder resin, (E) a photopolymerization initiator, and (C) a crosslinking agent, if necessary, in the form of a pigment dispersion, followed by mixing and dispersing in a ball mill or a roll mill using a ball mill or a roll mill. (F) a solvent or the like is added and mixed. The solvent (F) may be appropriately selected and used as long as it does not react with these components while dispersing or dissolving the components (A) to (C) or other components constituting the coloring composition and has appropriate volatility. In the preparation of the pigment dispersion, a solvent having a hydroxyl group (hereinafter also referred to as "solvent (f1)") and (f2) a solvent having no hydroxyl group (hereinafter referred to as " Solvent (f2) ") is preferably used in combination.

Of these 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- -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- Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol and cyclohexanol;

And ketoalcohols such as diacetone alcohol.

Among these solvents (f1), (poly) alkylene glycol monoalkyl ethers are preferable, and propylene glycol monomethyl ether and propylene glycol monoethyl ether are particularly preferable. The solvent (f1) may be used alone or in combination of two or more.

As the solvent f2, for example,

Ethylene glycol monomethyl ether acetate, 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 (Poly) alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate and 3-methyl- Acid esters;

Amyl acetate, n-butyl acetate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, propyl acetate, isopropyl acetate, n- , N-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

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

Among these solvents (f2), (poly) alkylene glycol monoalkyl ether acetates, ethers, ketones, diacetates and alkoxycarboxylic acid esters are preferable, and ethylene glycol monomethyl ether acetate, propylene glycol monomethyl But are not limited to, ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, Acetate, 1,6-hexanediol diacetate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate are preferred. The solvent (f2) may be used alone or in admixture of two or more.

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, Particularly preferably 5/95 to 25/75.

Although the content of the solvent is not particularly limited, it is preferably such that the total concentration of each component obtained by removing the solvent of the pigment dispersion or the coloring composition is 5 to 50% by mass, irrespective of whether it is a pigment dispersion or a colored composition, By mass to 40% by mass. By such an embodiment, it is possible to obtain a colorant dispersion having good dispersibility and stability, and a colored composition having good applicability and stability.

-additive-

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

Examples of the additive include fillers such as glass and alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as fluorine-based surfactants and silicone-based surfactants; Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like Adhesion promoters; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; An anti-aggregation agent such as sodium polyacrylate; Amino-1-pentanol, 3-amino-1,2-propane, 3-amino-1-pentanol, Diol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like; (Meth) acryloyloxyethyl] phthalate mono [2- (meth) acryloyloxyethyl], and omega -carboxypolycaprolactone mono (meth) .

Color filter and manufacturing method thereof

The color filter of the present invention comprises a colored layer formed using the coloring composition of the present invention.

As a method for manufacturing a color filter, first, the following method can be mentioned. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so as to partition a portion for forming a pixel as needed. Subsequently, a liquid composition of the radiation-sensitive composition of the present invention in which a red coloring agent containing, for example, a quinophthalone-based pigment is dispersed is applied onto the substrate, followed by prebaking to evaporate the solvent to form a coating film . Subsequently, this coating film is exposed through a photomask and then developed with an alkali developer to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed.

Subsequently, each of the coloring and radiation-sensitive compositions of green or blue was used to apply, bake, expose, develop and post-baking each of the coloring and radiation-sensitive compositions in the same manner as described above to form a green pixel array and a blue pixel array Are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

The black matrix may be formed by forming a desired thin film of metal such as chromium by sputtering or vapor deposition using a photolithography method. Alternatively, the black matrix may be formed by using a coloring and radiation- May be formed in the same manner as in the case of FIG.

Examples of the substrate used for forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.

These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition or the like depending on the purpose.

When the coloring and radiation-sensitive composition is applied to a substrate, a suitable coating method such as a spraying method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method or a bar coating method can be employed. , Slit die coating method is preferably employed.

Prebaking is usually carried out in combination with reduced pressure drying and heating and drying. The reduced-pressure drying is usually carried out until 50 to 200 Pa is reached. The conditions for heating and drying are usually about 70 to 110 DEG C for about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8 占 퐉, preferably 1.2 to 5 占 퐉, as a film thickness after drying.

Examples of the light source used for forming the pixel and / or the black matrix include a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, A laser light source such as an ion laser, a YAG laser, an XeCl excimer laser, and a nitrogen laser. An ultraviolet LED may be used as an exposure light source. Radiation with a wavelength in the range of 190 to 450 nm is preferred.

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

Examples of the alkali developer include sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] 1,5-diazabicyclo- [4.3.0] -5-nonene and the like are preferable.

A water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. may be added in an appropriate amount to the alkali developing solution. After the alkali development, it is usually washed with water.

As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid immersion) development method, and the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

The post-baking condition is usually about 180 to 280 DEG C for about 10 to 60 minutes.

The film thickness of the thus formed pixel is usually 0.5 to 5 占 퐉, preferably 1 to 3 占 퐉.

As a second method for manufacturing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Patent Laid-Open Nos. 7-318723 and 2000-310706 can do. In this method, a barrier wall serving also as a light shielding function is formed on the surface of a substrate. Subsequently, the liquid composition of the coloring composition of the present invention in which a red pigment is dispersed, for example, is ejected by an ink jet apparatus in the partition wall formed, and then the solvent is evaporated by prebaking. Subsequently, this coating film is exposed, if necessary, and then post-baked to form a red pixel pattern.

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

In addition, the barrier ribs function not only to shield the light-shielding function but also to prevent coloring compositions of the respective colors ejected into the compartment from being mixed, and thus the film thickness is thicker than that of the black matrix used in the first method. Therefore, the barrier rib is usually formed using a black radia radiation composition.

The substrate or radiation source used in forming the color filter, as well as the methods and conditions of prebaking and postbaking are the same as those of the first method described above. The film thickness of the pixel formed by the ink jet method is about the same as the thickness of the black matrix.

After forming a protective film on the thus-obtained pixel pattern as necessary, a transparent conductive film is formed by sputtering. After a transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation sensitive composition, and may be a spacer (black spacer) having light shielding properties. In this case, a coloring and radiation-sensitive composition in which a black coloring agent is dispersed is used, and the coloring composition of the present invention can be preferably used for forming such a black spacer.

The color filter of the present invention thus obtained is very useful for a color liquid crystal display element, a color image pickup tube element, a color sensor, an organic EL display element, and an electronic paper because of its extremely high luminance and color purity.

Display element

The display device of the present invention comprises the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and an electronic paper.

The color liquid crystal display device having the color filter of the present invention can take an appropriate structure. For example, a color filter may be formed on a substrate separate from a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which a driving substrate and a color filter are formed may be opposed via a liquid crystal layer 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, and a substrate on which an ITO (indium oxide doped with indium oxide) electrode is formed is opposed through a liquid crystal layer It is possible. The latter structure has an advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

The color liquid crystal display device having the color filter of the present invention may have a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). Examples of white LEDs include white LEDs that combine red LEDs, green LEDs, and blue LEDs to obtain white light by mixing colors, white LEDs that combine blue LEDs, red LEDs, and green phosphors to obtain white light by mixing colors, A white LED for obtaining a white light by mixing a red light emitting phosphor and a green light emitting phosphor and a white LED for obtaining a white light by mixing a blue LED and a YAG based phosphor; a combination of a blue LED and an orange light emitting phosphor and a green light emitting phosphor; A white LED for obtaining white light by mixing white light, an ultraviolet LED and a red LED, a white LED for obtaining a white light by mixing a green light emitting fluorescent substance and a blue light emitting fluorescent substance, and the like.

The color liquid crystal display device having the color filter of the present invention may be applied to a color liquid crystal display device such as TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Planes Switching) type, VA (Vertical Alignment) type, OCB (Optically Compensated Birefringence) Type liquid crystal mode can be applied.

Further, the organic EL display device having the color filter of the present invention can take an appropriate structure and can adopt a structure disclosed in, for example, Japanese Patent Application Laid-Open No. 11-307242.

Further, the electronic paper having the color filter of the present invention can have a suitable structure, for example, a structure disclosed in Japanese Patent Laid-Open No. 2007-41169.

<Examples>

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Measurement of Mw and Mw / Mn>

Mw and Mn of the copolymer (B) obtained in each of the following synthesis examples were measured by gel permeation chromatography (hereinafter referred to as GPC) of the following specifications. The measurement results are shown in Table 1 together with (B) the copolymerization ratio (mass%) of each monomer in the copolymer.

Apparatus: GPC-104 (manufactured by Showa Denko K.K.)

Column: KD-G, KF-603, KF-602 and KF-601 (manufactured by Showa Denko K.K.) were used in combination

Mobile phase: DMF

<Synthesis of (B) Copolymer>

Hereinafter, abbreviations of raw materials used in &quot; Synthesis of (B) Copolymer &quot;

THF: tetrahydrofuran

EEMA: 1-ethoxyethyl methacrylate

MA: methacrylic acid

nBMA: normal butyl methacrylate

MMA: methyl methacrylate

AIBN: 2,2'-azobisisobutyronitrile

DAMA: Dimethylaminoethyl methacrylate

CHMA: cyclohexyl methacrylate

BzMA: Benzyl methacrylate

PME-200: methoxypolyethylene glycol monomethacrylate (trade name: PME-200, manufactured by Nichiyu Kagaku Co., Ltd., n? 4 in the above formula (3)

PME-100: methoxypolyethylene glycol monomethacrylate (PME-100, n = 2 in the above formula (3), manufactured by Nichiyu Kagaku K.K.)

Synthesis Example 1

To a 1000 mL flask equipped with a stirrer, 516.1 g of THF, 34.1 g of lithium chloride (4.1% by weight concentration of THF solution) and 3.6 g of diphenylethylene were added and cooled to -60 캜. 9.2 g (15.4 mass% concentration hexane solution) of n-butyllithium was added and aged for 10 minutes. Thereafter, a mixture of 18.5 g of PME-200, 34.0 g of nBMA and 6.1 g of EEMA was added dropwise and the reaction was continued for 15 minutes.

Next, 55.4 g of DAMA was added dropwise. After the dropwise addition, the reaction was continued for 30 minutes, and then 3.2 g of methanol was added to stop the reaction. The obtained copolymer was adjusted to a 25 mass% concentration of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) solution, and then 114 g of water was added, and the mixture was heated to 100 캜 and reacted for 8 hours. By this reaction, EEMA was hydrolyzed to give a repeating unit derived from MA. The water was distilled off and adjusted to a PGMEA solution having a concentration of 40 mass%. Thus, a block copolymer comprising an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200, nBMA and MA was obtained. The obtained copolymer is referred to as &quot; copolymer (B-1) &quot;.

Synthesis Example 2

30 g of toluene, 4.2 g of PME-200, 5.6 g of MMA, 121 mg of AIBN and 312 mg of cyano (dimethyl) methyl ester of pyrazole-1-dithiocarboxylic acid were added and dissolved in a 300 mL flask equipped with a stirrer. Substitution was carried out. Thereafter, the temperature of the reaction solution was raised to 60 DEG C with gentle stirring, and this temperature was maintained for 24 hours to perform living radical polymerization.

Subsequently, 983 mg of AIBN and 18.2 g of DAMA were dissolved in 20 g of toluene, and the solution was subjected to nitrogen substitution for 30 minutes. The solution was added to the reaction solution, and subjected to living radical polymerization at 60 DEG C for 24 hours. Thereafter, the solution was adjusted to a 40% by mass concentration of PGMEA solution by concentration under reduced pressure. Thus, a block copolymer comprising a block A having a repeating unit derived from DAMA and a block B having a repeating unit derived from PME-200 and MMA was obtained. The obtained block copolymer is referred to as &quot; copolymer (B-2) &quot;.

Synthesis Example 3

In a 2000 mL flask equipped with a stirrer, 987.6 g of THF and 51.4 g of lithium chloride (3.9 mass% concentration of THF solution) were added and cooled to -60 캜. After 21.4 g (15.4 mass% concentration hexane solution) of n-butyllithium was added and stirred for 10 minutes, 4.9 g of diisopropylamine was added and the mixture was stirred for 15 minutes. Then, 4.7 g of methyl isobutyrate was added, Respectively. 87.9 g of MMA and 45.3 g of PME-200 were added dropwise, and the reaction was continued for 15 minutes.

Next, 133.6 g of DAMA was added dropwise. After the dropwise addition, the reaction was continued for 30 minutes, and then 7.7 g of methanol was added to stop the reaction. The obtained copolymer was adjusted to a PGMEA solution having a concentration of 40 mass%. Thus, a block copolymer comprising a block A having a repeating unit derived from DAMA and a block B having a repeating unit derived from PME-200 and MMA was obtained. The obtained copolymer is referred to as &quot; Copolymer (B-3) &quot;.

Synthesis Example 4

30 g of toluene, 7.6 g of nBMA, 9.2 g of PME-200, 174 mg of AIBN and 449 mg of cyano (dimethyl) methyl ester of pyrazole-1-dithiocarboxylic acid were added and dissolved in a 300 mL flask equipped with a stirrer. Substitution was carried out. Thereafter, the temperature of the reaction solution was raised to 60 DEG C with gentle stirring, and this temperature was maintained for 24 hours to perform living radical polymerization.

Subsequently, 716 mg of AIBN and 11.2 g of DAMA were dissolved in 20 g of toluene, and the solution was subjected to nitrogen substitution for 30 minutes. The solution was added to the reaction solution, and subjected to living radical polymerization at 60 DEG C for 24 hours. Thereafter, the solution was adjusted to a 40% by mass concentration of PGMEA solution by concentration under reduced pressure. Thus, a block copolymer consisting of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200 and nBMA was obtained. The obtained block copolymer is referred to as &quot; copolymer (B-4) &quot;.

Synthesis Example 5

20 g of toluene, 187 mg of AIBN and 12.3 g of DAMA were added to a 300-mL flask equipped with a stirrer and dissolved therein, followed by nitrogen substitution for 30 minutes. Thereafter, the temperature of the reaction solution was raised to 60 DEG C with gentle stirring, and this temperature was maintained for 24 hours to perform living radical polymerization.

Subsequently, 2.2 g of MMA, 7.0 g of PME-200, 5.6 g of CHMA, 0.89 g of MA, 809 mg of AIBN and 461 mg of cyano (dimethyl) methyl ester of pyrazole-1-dithiocarboxylic acid were dissolved in 30 g of toluene, A nitrogen-substituted solution was added to the reaction solution, and living radical polymerization was carried out at 60 캜 for 24 hours. Thereafter, the solution was adjusted to a 40% by mass concentration of PGMEA solution by concentration under reduced pressure. Thus, a block copolymer comprising an A block having repeating units derived from DAMA and a B block having repeating units derived from PME-200, MMA, CHMA, and MA was obtained. The obtained block copolymer is referred to as &quot; copolymer (B-5) &quot;.

Synthesis Example 6

In a 1000 mL flask equipped with a stirrer, 503.0 g of THF and 59.5 g of lithium chloride (4.1% by weight concentration of THF solution) were added and cooled to -60 캜. (15.9 mass% concentration hexane solution) was added and stirred for 10 minutes. Then, diisopropylamine (2.8 g) was added and stirred for 15 minutes, followed by addition of 2.8 g of methyl isobutyrate and further stirring for 15 minutes Respectively. 74.6 g of MMA and 32.2 g of PME-100 were added dropwise and the reaction was continued for 15 minutes.

Next, 52.1 g of DAMA was added dropwise, the reaction was continued for 30 minutes after dropwise addition, and then 4.5 g of methanol was added to stop the reaction. The obtained copolymer was adjusted to a PGMEA solution having a concentration of 40 mass%. Thus, a block copolymer comprising a block A having a repeating unit derived from DAMA and a block B having a repeating unit derived from PME-200 and MMA was obtained. The obtained copolymer is referred to as &quot; Copolymer (B-6) &quot;.

Comparative Synthesis Example 1

30 g of toluene, 5.6 g of PME-200, 13.1 g of BzMA, 196 mg of AIBN and 506 mg of cyano (dimethyl) methyl ester of pyrazole-1-dithiocarboxylic acid were added and dissolved in a 300 mL flask equipped with a stirrer. Substitution was carried out. Thereafter, the temperature of the reaction solution was raised to 60 DEG C with gentle stirring, and this temperature was maintained for 24 hours to perform living radical polymerization.

Subsequently, 607 mg of AIBN and 9.2 g of DAMA were dissolved in 20 g of toluene, and the solution was subjected to nitrogen substitution for 30 minutes. The solution was added to the reaction solution and subjected to living radical polymerization at 60 ° C for 24 hours. Thereafter, the solution was adjusted to a 40% by mass concentration of PGMEA solution by concentration under reduced pressure. Thus, a block copolymer comprising an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200 and BzMA was obtained. The obtained block copolymer is referred to as &quot; copolymer (b-1) &quot;.

Comparative Synthesis Example 2

In a 1000 mL flask equipped with a stirrer, 498.6 g of THF and 42.5 g of lithium chloride (4.1 mass% concentration of THF solution) were added and cooled to -60 캜. 8.7 g (15.4 mass% concentration hexane solution) of n-butyllithium was added and stirred for 10 minutes. Then, 1.8 g of diisopropylamine was added and stirred for 15 minutes. Subsequently, 1.8 g of methyl isobutyrate was added and stirred for 15 minutes Respectively. A mixed solution of 60.7 g of MMA, 33.6 g of PME-200 and 11.8 g of EEMA was added dropwise and the reaction was continued for 15 minutes.

Then, 28.7 g of DAMA was added dropwise. After the dropwise addition, the reaction was continued for 30 minutes, and then 2.4 g of water was added to terminate the reaction. The obtained copolymer was adjusted to a PGMEA solution having a concentration of 25 mass%, and then 135 g of water was added, and the mixture was heated to 100 DEG C and reacted for 8 hours. By this reaction, EEMA hydrolyzes and repeating units derived from MA are formed. The water was distilled off and adjusted to a PGMEA solution having a concentration of 40 mass%. Thus, a block copolymer comprising an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200, MMA and MA was obtained. The obtained block copolymer is referred to as &quot; copolymer (b-2) &quot;.

Comparative Synthesis Example 3

20 g of toluene, 66 mg of AIBN and 21.0 g of DAMA were added to a 300-mL flask equipped with a stirrer and dissolved, followed by nitrogen substitution for 30 minutes. Thereafter, the reaction solution was slowly stirred to raise the temperature of the reaction solution to 60 DEG C, and this temperature was maintained for 24 hours to perform living radical polymerization.

Subsequently, a solution obtained by dissolving 2.8 g of nBMA, 4.2 g of PME-200, 1259 mg of AIBN and 170 mg of cyano (dimethyl) methyl ester of pyrazole-1-dithiocarboxylic acid in 30 g of toluene followed by nitrogen substitution for 30 minutes was subjected to the above reaction Solution, and subjected to living radical polymerization at 60 占 폚 for 24 hours. Thereafter, the solution was adjusted to a 40% by mass concentration of PGMEA solution by concentration under reduced pressure. Thus, a block copolymer consisting of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200 and nBMA was obtained. The obtained block copolymer is referred to as &quot; copolymer (b-3) &quot;.

&Lt; Measurement of acid value &

The acid value of the (B) copolymer obtained in each of the above Synthesis Examples was measured in the following manner. Table 1 shows the measurement results.

0.5 g of the copolymer solution was precisely weighed to a unit of 1 mg and collected into a glass container. After diluting with 50 ml of propylene glycol monomethyl ether acetate, phenolphthalein was added and titration was carried out with 0.1 N ethanolic aqueous potassium hydroxide solution to obtain a pink colored end point. A blank test was similarly conducted. The acid value (unit: mgKOH / g) was calculated from the amount of 0.1N aqueous ethanolic potassium hydroxide aqueous solution of the (B) copolymer and the blank test.

<Measurement of amine value>

The amine value of the (B) copolymer obtained in each Synthesis Example was measured in the following manner. Table 1 shows the measurement results.

0.5 g of the copolymer solution was precisely weighed to a unit of 1 mg and collected into a glass container. 20 mL of anhydrous acetic acid / acetic acid = 9/1 (volume ratio) was added and dissolved, and the mixture was allowed to stand at room temperature for 3 hours. Thereafter, 30 mL of acetic acid was further added, and titration was performed with a 0.1 mol / L perchloric acid / acetic acid solution using a potential difference measuring device AT-510 (manufactured by Kyoto Denshi Kogyo Co., Ltd.). A blank test was similarly conducted. (Unit: mgKOH / g) was calculated from the drop amount of 0.1 mol / L perchloric acid / acetic acid solution of the copolymer (B) and the blank test.

&Lt; Production of Pigment Dispersion >

Production Example 1

, 12 parts by mass of CI Pigment Green 58 (manufactured by DIC) and 3 parts by mass of CI Pigment Yellow 138 as a colorant, 10 parts by mass of a copolymer (B-1) solution (nonvolatile component = 40% by mass) 67 parts by mass of propylene glycol monomethyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether were treated with a bead mill to prepare a pigment dispersion (A-1).

Production Examples 2 to 6 and Comparative Production Examples 1 to 3

Pigment dispersions (A-2) to (A-9) were prepared in the same manner as in Production Example 1 except that the kind of the copolymer (B) was changed as shown in Table 2 in Production Example 1.

&Lt; Evaluation of Pigment Dispersion >

The viscosity of the resultant pigment dispersion was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Further, the resulting colorant dispersion was filled in a light-shielding glass container and allowed to stand in a closed state at 23 DEG C for 14 days, and then the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). "A" represents a case where the increase rate is less than 5%, "B" represents a case where the increase rate is less than 10%, "C" represents a case where the increase rate is 10% or more, . The evaluation results are shown in Table 2.

In Table 2, &quot; G58 &quot; means CI Pigment Green 58, &quot; Y138 &quot; means CI Pigment Yellow 138, &quot; PGMEA &quot; means propylene glycol monomethyl ether acetate, and &quot; PGME &quot; means propylene glycol monomethyl ether do.

&Lt; Synthesis of binder resin >

Synthesis Example 7

30.0 g of BzMA, 20.0 g of nBMA, 15.0 g of hydroxyethyl methacrylate, 20.0 g of styrene, 15.0 g of MA and 200 g of PGMEA were added to and dissolved in a flask equipped with a cooling tube and a stirrer, and 3.0 g of AIBN and? 5.0 g of styrene dimer was added, and then nitrogen substitution was performed for 15 minutes. Thereafter, the reaction solution was heated to 80 캜 with stirring and polymerized for 5 hours to obtain a solution containing 33% by mass of the binder resin (D-1). The binder resin (D-1) had a weight average molecular weight of 10,000 as measured by GPC (mobile phase: tetrahydrofuran) in terms of polystyrene, and a ratio of weight average molecular weight to number average molecular weight of 2.5.

Synthesis Example 8

In a flask equipped with a cooling tube and a stirrer, 25.0 g of 3-methacryloyloxymethyl-3-ethyloxetane, 18.0 g of MA, 9.0 g of mono 2-acryloxyethyl succinate, 10.0 g of N-phenylmaleimide, g, 14.0 g of hydroxyethyl methacrylate and 300 g of PGMEA were added and dissolved, and 6.0 g of AIBN and 6.0 g of? -methylstyrene dimer were added, followed by nitrogen substitution for 15 minutes. Thereafter, the reaction solution was heated to 80 캜 with stirring and polymerized for 5 hours to obtain a precursor copolymer solution.

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

&Lt; Preparation and evaluation of colored composition >

Preparation of coloring composition

Example 1

100 parts by mass of the pigment dispersion (A-1), 13.4 parts by mass of the binder resin (D-1) solution as the binder resin, and 5.0 parts by mass of MAX-3510 (dipentaerythritol hexaacrylate as a main component) manufactured by Nippon Kayaku Kabushiki Kaisha 2.8 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, , 0.3 part by mass of Megapac F-554 (manufactured by DIC Co.) and 126.5 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed to prepare a liquid color composition.

Evaluation of chromaticity characteristics

The obtained coloring composition was coated on a glass substrate using a spin coater and prebaked on a hot plate at 90 DEG C for 2 minutes to form three coating films having different film thicknesses. Subsequently, these substrates were cooled to room temperature, and then a coating film on the substrate was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm on each coating film using a high-pressure mercury lamp at an exposure amount of 1,000 J / m ² Lt; / RTI &gt; Thereafter, post-baking was performed at 230 캜 for 60 minutes to form a cured film on the substrate. The chromaticity coordinate values (x, y) and the magnetic pole value (Y) in the CIE colorimetric system at the 2-degree field are measured using a color analyzer (MCPD2000 manufactured by Otsuka Denshi Co., Ltd.) Respectively. The chromaticity coordinate value x and the stimulus value (Y) at the chromaticity coordinate value y = 0.569 were obtained from the measurement results. The evaluation results are shown in Table 3. The larger the value of the stimulus value Y, the higher the luminance.

Evaluation of contrast

The three cured films obtained in the &quot; Evaluation of Chrominance Characteristics &quot; were measured for contrast using a contrast meter (CT-1 manufactured by Tsubosaka Denshi Co., Ltd.). From the measurement result, the contrast at the chromaticity coordinate value y = 0.569 was obtained. The evaluation results are shown in Table 3. The larger the value, the higher the contrast.

Examples 2 to 6 and Comparative Examples 1 to 3

A coloring composition was prepared and evaluated in the same manner as in Example 1 except that the pigment dispersion, binder resin, crosslinking agent, photopolymerization initiator and solvent were changed as shown in Table 3. The evaluation results are shown in Table 3.

The components in Table 3 are as follows.

C-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name MAX-3510, manufactured by Nippon Kayaku Kabushiki Kaisha)

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

E-1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- acetyloxime) (trade name Irgacure OXE02, Manufactured by Specialty Chemicals)

E-2: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369, manufactured by Ciba Specialty Chemicals)

EEP: ethyl 3-ethoxypropionate

MBA: 3-methoxybutylacetate

Claims (8)

(A), (B) and (C);
(A) a colorant comprising a quinophthalone-based pigment,
(B) a polymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit having an acidic group or a repeating unit represented by the following formula (3) To 232 mg KOH / g, and
(C) Crosslinking agent
And a coloring composition for a color filter.

[In the formula (1)
R ¹ represents a hydrogen atom or a methyl group,
Z represents -NR ² R ³ (wherein R ² and R ³ independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group) or a substituted or unsubstituted nitrogen-containing heterocyclic group,
X &lt; ¹ &gt; represents a divalent linking group]

[In the formula (2)
R ⁴ represents a hydrogen atom or a methyl group,
R &lt; ⁵ &gt; represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

[In the formula (3)
R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ independently represents an alkanediyl group having 2 to 4 carbon atoms,
R ⁸ represents an alkyl group having 1 to 6 carbon atoms,
and n represents an integer of 1 to 150) The coloring composition according to claim 1, wherein the quinophthalone-based pigment is CI Pigment Yellow 138. The coloring composition for a color filter according to claim 1, further comprising (D) a binder resin (excluding the above component (B)). The coloring composition for a color filter according to claim 1, further comprising (E) a photopolymerization initiator. A color filter comprising a colored layer formed using the colored composition according to any one of claims 1 to 4. A display element comprising the color filter according to claim 5. The following components (a1), (B) and (F);
(a1) a quinophthalone-based pigment,
(B) a polymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit having an acidic group or a repeating unit represented by the following formula (3) To 232 mg KOH / g, and
(F) Solvent
And a pigment dispersed in the pigment dispersion.

[In the formula (1)
R ¹ represents a hydrogen atom or a methyl group,
Z represents -NR ² R ³ (wherein R ² and R ³ independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group) or a substituted or unsubstituted nitrogen-containing heterocyclic group,
X &lt; ¹ &gt; represents a divalent linking group]

[In the formula (2)
R ⁴ represents a hydrogen atom or a methyl group,
R &lt; ⁵ &gt; represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

[In the formula (3)
R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ independently represents an alkanediyl group having 2 to 4 carbon atoms,
R ⁸ represents an alkyl group having 1 to 6 carbon atoms,
and n represents an integer of 1 to 150) delete