KR101886870B1 - Coloring composition for color filter, color filter and display device - Google Patents

Abstract

<화학식 2>

〔화학식 1에 있어서, R¹은 수소 원자 또는 메틸기를 나타내고, Z는 -N⁺R²R³R⁴Y^-(단, R² 내지 R⁴는 서로 독립적으로 수소 원자 또는 탄화수소기를 나타내고, R² 내지 R⁴ 중 2개 이상이 서로 결합하여 포화 복소환을 형성할 수도 있고, Y^-는 상대 음이온을 나타냄), 또는 -NR⁵R⁶(단, R⁵ 및 R⁶은 서로 독립적으로 수소 원자 또는 탄화수소기를 나타내고, R⁵ 및 R⁶이 서로 결합하여 포화 복소환을 형성할 수도 있음)을 나타내고, X¹은 2가의 연결기를 나타내고, 화학식 2에 있어서, R⁷은 수소 원자 또는 메틸기를 나타내고, R⁸은 지방족 탄화수소기 또는 지환식 탄화수소기를 나타냄〕An object of the present invention is to provide a coloring composition for a color filter which is excellent in chromaticity characteristics and is excellent in developing property and storage stability.
The solution of the invention comprises the following components (A), (B) and (C);
(A) a colorant containing a pigment,
(1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group, wherein the repeating unit (1) (Mw / Mn) of from 1.0 to 1.9 and a copolymerization ratio of the repeating unit (2) to the sum of the weight average molecular weight Mw and the number average molecular weight Mn is not less than 75 mass%
(C) Crosslinking agent
Wherein the coloring composition is a coloring composition for a color filter.
&Lt; Formula 1 >

(2)

Wherein R ¹ represents a hydrogen atom or a methyl group, Z represents -N ⁺ R ² R ³ R ⁴ Y ^- (wherein R ² to R ⁴ independently represent a hydrogen atom or a hydrocarbon group, and R ² To R ⁴ may combine with each other to form a saturated heterocycle, and Y ^- represents a counter anion), or -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom or R ⁵ and R ⁶ may be bonded to each other to form a saturated heterocycle, X ¹ represents a divalent linking group, R ⁷ represents a hydrogen atom or a methyl group, R ⁸ 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,

BACKGROUND OF THE INVENTION 1. Field of the Invention 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 transmission type or reflection type color liquid crystal display device, A coloring composition used for forming a coloring layer, a color filter having a coloring layer formed using the coloring composition, and a display device having the color filter.

In the production of a color filter using the coloring and radiation-sensitive composition, a pigment-dispersed coloring and radiation-sensitive composition is applied onto a substrate and dried, and then the dry film is irradiated with a desired pattern (hereinafter, (Hereinafter, referred to as &quot; color images &quot;) and then developing them to obtain pixels of respective colors (Patent Documents 1 and 2). A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known. There is also known a method of obtaining pixels of respective colors by an ink jet method using a pigment dispersion type colored resin composition (Patent Document 4).

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

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 a demand for high contrast, high color purity, and high brightness of recent color liquid crystal display devices, and further, It is hard to say that many problems such as the problem are solved. Therefore, there is a strong demand for 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 developability and the like.

Accordingly, an object of the present invention is to provide a coloring composition for a color filter which is excellent in chromaticity characteristics, and is excellent in developing property and storage stability. Another object of the present invention is to provide a color filter comprising a colored layer formed from 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 found that the above problems can be solved by using a block copolymer having a specific repeating unit, and the present invention has been completed.

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

(A) a colorant containing a pigment,

(1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group, wherein the repeating unit (1) (Hereinafter referred to as &quot; (B) a copolymer having a copolymerization ratio of the repeating unit (2) with respect to the total of the repeating units (A) and (B) of 75% by mass or more and a ratio (Mw / ) Copolymer &quot;), and

(C) Crosslinking agent

And a coloring composition for a color filter.

Wherein R ¹ represents a hydrogen atom or a methyl group, Z represents -N ⁺ R ² R ³ R ⁴ Y ^- (wherein R ² to R ⁴ independently represent a hydrogen atom or a hydrocarbon group, and R ² To R ⁴ may combine with each other to form a saturated heterocycle, and Y ^- represents a counter anion), or -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom or And R &lt; ⁵ &gt; and R &lt; ⁶ &gt; may combine with each other to form a saturated heterocycle), and X &lt; ¹ &gt; represents a divalent linking group.

[In the formula (2), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

The present invention also provides a color filter comprising a coloring layer formed using the coloring composition, and a display element comprising the color filter. Here, the &quot; colored layer &quot; 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 pigment,

The (B) copolymer, and

(F) Solvent

To provide a pigment dispersion for a color filter.

INDUSTRIAL APPLICABILITY The coloring composition for a color filter of the present invention is excellent in chromaticity characteristics, and has excellent developability 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 &quot; coloring composition &quot;) will be described.

- (A) Colorant -

The coloring composition of the present invention contains (A) a pigment (a1) as a colorant. The (a1) pigment is not particularly limited and may be any of organic pigments and inorganic pigments. In the present invention, (a1) pigments may be used alone or in admixture of two or more. Of course, an organic pigment and an inorganic pigment may be mixed and used.

Examples of the organic pigment include compounds classified by pigment in the color index (published by CI., The Society of Dyers and Colourists). Specifically, the color index (C.I.) name is attached as follows.

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

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

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

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

C.I. Pigment Blue 1, C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 60, C.I. Pigment Blue 80;

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

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

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

Examples of the inorganic pigments include inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, spinach (red iron oxide (III)), cadmium, Cobalt rust, amber, titanium black, synthetic iron black, and carbon black.

In the present invention, (a1) the pigment may be purified and used by recrystallization, reprecipitation, solvent cleaning, sublimation, vacuum heating, or a combination thereof. Further, (a1) the pigment may be used by modifying its particle surface with a resin, if desired. (a1) As the resin for modifying the particle surface of the pigment, for example, a vehicle resin described in Japanese Patent Application Laid-Open No. 2001-108817 or a commercially available resin for dispersing various pigments may 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. Further, it is preferable that the organic pigment is 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.

By using a dye as a coloring agent in a coloring composition for a color filter, high brightness and high contrast that can not be attained by a pigment alone can be achieved. However, when the (a2) dye is used as the coloring agent, the alkali developability of the coloring composition is remarkably deteriorated. On the other hand, by using the (B) copolymer as the pigment dispersant in the coloring composition of the present invention, it is possible to obtain a coloring composition having good alkali developing property even when the pigment (a1) and the dye (a2) have.

As the dye (a2), for example, a compound having the following color index (C.I.) name can be mentioned.

C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Molten Red 7, C.I. Molten Yellow 5, C.I. Azo dyes such as Mordant Black 7;

C.I. Pad Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Anthraquinone type dyes such as Disperse 60;

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

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

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

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

Disperse Yellow 201 and the like.

When the dye (a2) is used as the colorant in the present invention, the dye (a2) may be used singly or in a mixture of two or more.

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, from the viewpoint of forming a pixel having a high luminance and excellent color purity or a black matrix having excellent light- . Here, the solid content is a component other than the solvent described later.

- (B) Copolymer -

The copolymer (B) in the present invention has a repeating unit (1), a repeating unit (2) and a repeating unit (3), and the content of the repeating unit (2) (Mw / Mn) of from 1.0 to 1.9 in terms of the weight average molecular weight Mw and the number average molecular weight Mn, but functions as a dispersant for the colorant (A). Here, Mw and Mn refer to the weight average molecular weight and the number average molecular weight in terms of polymethylmethacrylate measured by gel permeation chromatography (GPC, elution solvent: DMF).

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

In Formula 1, R ¹ is preferably a hydrogen atom or a methyl group in the methyl group.

Also, Z is ^{-N + R 2 R 3 R 4} Y - or -NR represents a ⁵ R ^6, R ² to R ⁶ is represents a hydrogen atom or a hydrocarbon group independently of each other, "hydrocarbon group" in the present invention is, 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, and may contain an unsaturated bond in the molecule It can be anywhere.

The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms), more specifically an alkyl group having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms), an aliphatic hydrocarbon group having 2 to 20 carbon atoms Is an alkenyl group of 2 to 12 carbon atoms, and an alkynyl group of 2 to 20 carbon atoms (preferably 2 to 12 carbon atoms). The alicyclic hydrocarbon is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms (preferably 3 to 12 carbon atoms), more specifically, a cycloalkyl group having 3 to 20 carbon atoms (preferably 3 to 12 carbon atoms) . The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms), more specifically an aryl group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) and an aromatic hydrocarbon group having 7 to 16 carbon atoms (Preferably 7 to 12) aralkyl groups. Here, in the present invention, the "aryl group" refers to a monocyclic to tricyclic aromatic hydrocarbon group.

Among them, the hydrocarbon group in R ² to R ⁶ is preferably an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms) or an aralkyl group having 7 to 16 carbon atoms (preferably 7 to 12 carbon atoms) An ethyl group, a propyl group, a butyl group, and a benzyl group are particularly preferable.

Examples of the saturated heterocyclic ring formed by combining two or more of R ² to R ⁴ in the above formula (1) include the following.

In the formula (1-1), R represents a hydrogen atom or a hydrocarbon group, "*" represents a bond, and the hydrocarbon group for R may be the same as the above-mentioned R ² .

Examples of the saturated heterocycle in which R ⁵ and R ⁶ are bonded to each other in the above formula (1) include the followings.

In the formula (1-2), &quot; * &quot; represents a bonding hand.

Examples of the divalent linking group (X ¹ ) in the general formula ( ¹ ) include a methylene group, an alkylene group having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, an arylene group, a -CONH-R ¹¹ group, -R ¹² -group, and the like. Here, R ¹¹ and R ¹² independently represent a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6 carbon atoms), or an ether group (alkyleneoxyalkylene group) having 2 to 10 carbon atoms. Among them, X ¹ is preferably a -COO-R ¹² group, and R ¹² is preferably an alkylene group having 2 to 6 carbon atoms.

In the general formula (1), Y ^- may be a halogen ion such as Cl ^- , Br ^- or I ^-, or a counter anion of an acid such as ClO ₄ ^- , BF ₄ ^- , CH ₃ COO ^- or PF ₆ ^- .

In the general formula (2), R ⁷ is preferably a hydrogen atom or a methyl group in the methyl group.

Examples of the aliphatic hydrocarbon group for R ⁸ include an alkyl group, an alkenyl group and an alkynyl group. Among them, R ⁸ is preferably an alkyl group having 1 to 15 carbon atoms (preferably 1 to 12 carbon atoms), more preferably a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, A decyl group, and a dodecyl group are particularly preferable.

Examples of the alicyclic hydrocarbon group for R ⁸ 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. Among them, R ⁸ is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms (preferably 4 to 15 carbon atoms), and is preferably a cyclohexyl group, a t-butylcyclohexyl group, a decahydro-2-naphthyl group or a tricyclo [5.2. 1.0 ^2,6 ] decan-8-yl group, adamantyl group, dicyclopentenyl group, pentacyclopentadecanyl group, tricyclopentenyl group and isobornyl group are particularly preferable.

The repeating unit (3) is gatjiman 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, the acidic group is preferably a phenolic hydroxyl group or a carboxyl group in view of dispersibility and alkali developability of the resulting colored composition, and particularly preferably a carboxyl group.

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

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

In the general formula (3), R ¹⁰ is preferably a hydrogen atom or a methyl group in the methyl group.

Examples of the divalent linking group (X ² ) include a methylene group, an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6 carbon atoms), an arylene group, a -CONH-R ¹³ group, a -COO-R ¹⁴ group, -OCOR ¹⁵ group, -R ¹⁶ -OCO-R ¹⁷ -, -COO- (C _m H _2m COO) ₁ -C _m H _2m group, -COO-R ¹⁸ -OCO-R ¹⁹ - have. Here, R ¹³ to R ¹⁷ independently represent a single bond, a methylene group, an alkylene group having 2 to 10 (preferably 2 to 6) carbon atoms or an ether (alkyleneoxyalkylene) group having 2 to 10 carbon atoms , m is an integer of 1 to 10, 1 is an integer of 1 to 4, R ¹⁸ is a methylene group or an alkylene group having 2 to 10 (preferably 2 to 6) carbon atoms, and R ¹⁹ is a single bond , A methylene group, an alkylene group having 2 to 10 (preferably 2 to 6) carbon atoms, a cyclohexane-1,2-diyl group or a phenylene group (for example, a 1,2- ).

Among these, X ² as a single bond, phenylene group, -COO-R ¹⁴ - _{group, -COO- (C m H 2m COO} ) l -C m H 2m - group or ^{-COO-R 18 -OCO-R 19} - .

(B) copolymer may have a repeating unit other than the above (hereinafter referred to as "repeating unit (4)"). Examples of such a repeating unit (4) include ethylenic unsaturation having a nitrogen-containing unsaturated heterocyclic group such as a pyridyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, an imidazolinyl group or a tetrahydropyrimidinyl group Monomers; Styrene-based monomers such as styrene and? -Methylstyrene; (Meth) acrylamide; Vinyl acetate; A repeating unit derived from a monomer such as acrylonitrile, and a repeating unit represented by the following formula (4). Here, in the present invention, "(meth) acrylate" means "acrylate or methacrylate".

In formula (4), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents an alkylene group having 2 to 4 carbon atoms, and R ²² represents an alkyl group having 1 to 6 carbon atoms.

In the copolymer (B), the copolymerization ratio of the repeating unit (1) is preferably 5 to 70 mass%, more preferably 10 to 60 mass%, still more preferably 15 to 40 mass% to be. The copolymerization ratio of the repeating unit (2) is 75% by mass or more, preferably 75 to 99% by mass, more preferably 80 to 99% by mass, still more preferably 75% By mass to 85% by mass to 99% by mass, and particularly preferably 90% by mass to 99% by mass. The copolymerization ratio of the repeating unit (3) is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and particularly preferably 1 to 10% by mass, relative to the total of the repeating units other than the repeating unit (1) %to be. By copolymerizing the respective repeating units at such a ratio, a colored composition excellent in dispersibility and alkali developability can be obtained.

The acid value of the (B) copolymer is preferably 5 to 70 mgKOH / g, more preferably 10 to 55 mgKOH / g, and particularly preferably 15 to 45 mgKOH / g in terms of storage stability. Here, in the present invention, the "acid value" means the number of mg of KOH required to neutralize 1 g of the non-volatile component excluding the solvent of the copolymer solution, specifically, the value measured by the method described in the following example.

The amine value of the (B) copolymer is preferably 10 to 200 mgKOH / g, more preferably 30 to 170 mgKOH / g, and particularly preferably 50 to 150 mgKOH / g in terms of storage stability. Herein, 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 component excluding the solvent of the copolymer solution, specifically, the value measured by the method described in the following Examples It says.

The copolymer (B) is not particularly limited as long as it has the repeating unit (1) to the repeating unit (3), but it is preferable that the repeating unit (2) Is preferably a block copolymer comprising an A block having a unit (1) and a B block having no repeating unit (1) and having a repeating unit (2) and a repeating unit (3). The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. In this case, the copolymerization ratio (mass ratio) of the A block / B block is preferably 5/95 to 70/30, more preferably 10/90 to 60/40, and particularly preferably 15/85 to 40/60.

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 are included in the A blocks in any of random copolymerization and block copolymerization Can be.

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 an ethylenically unsaturated monomer having the nitrogen-containing unsaturated heterocyclic group.

On the other hand, in the B block, the repeating unit (2) and the repeating unit (3) may be contained in any of random copolymerization and block copolymerization. When the (B) copolymer is a BAB block copolymer, a B1 block having a repeating unit (2) and no repeating unit (3) and a B2 block having a repeating unit (3) B1-A-B2 block copolymer. The repeating unit (2) and the repeating unit (3) may contain two or more kinds of repeating units in each of the B blocks. In this case, each repeating unit may be either random copolymerization or block copolymerization May also be included.

The repeating units other than the repeating unit (2) and the repeating unit (3) may be contained in the B block. Examples of such repeating units include styrene-based monomers such as styrene and? -Methylstyrene; (Meth) acrylamide; Vinyl acetate; A repeating unit derived from a monomer such as acrylonitrile, and a repeating unit represented by the above formula (4).

The total copolymerization ratio of the repeating unit (2) and the repeating unit (3) in the B block is preferably 76% by mass or more, more preferably 83% by mass or more, and particularly preferably 100% by mass.

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

The copolymer (B) can be produced by a known method, but when the copolymer (B) is a block copolymer, it can be produced, for example, by living polymerization of a monomer introducing each of the repeating units. As a living polymerization method, 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) S; Ute Kochi, Hatadakoichi, Polymer Processing, 36, 366 (1987); Toshinobu Higashimura, Sawamoto Mitsuo, Polymer Ron Collection, 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Soc., 109, 4737 (1987); Ida Takuzo, Inoue Shohei, Organic Synthetic 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. A Polym. Chem., 47, 3544-3557 (2009).

Examples of the monomer providing the repeating unit (1) include (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride , (Meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride, dimethylaminoethyl (Meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. These may be used alone or in combination of two or more. The repeating unit (1) wherein Z is -N ⁺ R ² R ³ R ⁴ Y ^- is obtained by polymerizing a monomer (for example, dimethylaminoethyl (meth) acrylate) wherein Z is -NR ⁵ R ⁶ , It is also possible to react the above polymer with a halogenated hydrocarbon compound such as benzyl chloride to partially quaternize the amino group.

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 (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, (meth) acrylic acid carboxymethyl ester, (meth) Esters, mono [2- (meth) acryloyloxyethyl] succinate, ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylbenzoic acid, p- hydroxystyrene, p- Acryloyloxyethylsulfonic acid, 2-acryloyloxyethylsulfonic acid, 2-methacryloxyethylsulfonic acid, sodium 2-acryloyloxyethylsulfonate, lithium 2-acryloyloxyethylsulfonate, ammonium 2- Acryloyloxyethylsulfonic acid imidazolium, 2-acryloyloxyethylsulfonylpyridinium, 2-methacryloxyethylsulfonic acid sodium, 2-methacryloxyethylsulfonic acid lithium, 2-methacryloxyethylsulfonic acid ammonium, 2- Methacryloxyethylsulfonic acid imidazolium, 2-methacrylic Pyridinium oxyethylsulfonate, styrenesulfonic acid, sodium styrenesulfonate, lithium styrenesulfonate, ammonium styrenesulfonate, imidazolium styrenesulfonate, and pyridinium styrenesulfonate. These may be used alone or in combination of two or more.

Examples of the ethylenically unsaturated monomer having an unsaturated heterocyclic group having nitrogen atom in the monomer providing the repeating unit (4) include the following compound groups? (Monomers 1 to 18), the compound group? (Monomers 19 to 20 ), And the like.

[Compound group?]

Examples of the monomer providing the repeating unit represented by the formula (4) among the monomers providing the repeating unit (4) include 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) Methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, and the like.

(B) may be used alone or in combination of two or more. The content of the (B) copolymer 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 (a1) pigment. If the content of the copolymer (B) is too large, the developability may be impaired.

In the present invention, a further known dispersant may be contained in order to improve 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), urethane dispersants Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170 and Disperbyk-182 (manufactured by BYK) (Manufactured by Ajinomoto Fine Techno Co., Ltd.) as a polyethylene imine dispersing agent, and a polyester dispersing agent such as Azisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.) ) And the like. Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

- (C) Crosslinking agent -

In the present invention, the (C) crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an 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-alkoxymethyl amino 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 modified with an alkylene oxide and a polyfunctional (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, a (meth) acrylate having a hydroxyl group and an acid anhydride And a polyfunctional (meth) acrylate having a carboxyl group obtained by the reaction.

Examples of the aliphatic polyhydroxy compound include aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, aliphatic polyhydroxy compounds such as glycerin, trimethylol propane, pentaerythritol, dipentaerythritol Trivalent or higher aliphatic polyhydroxy compounds. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, and glycerol 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 JP-A-11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide and / or propylene oxide modified di (meth) acrylate of bisphenol A, ethylene oxide and / or propylene oxide modified tree of isocyanuric acid (Meth) acrylate of trimethylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of trimethylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, Ethylene oxide and / or propylene oxide modified penta (meth) acrylate of dipentaerythritol, ethylene oxide of dipentaerythritol, and ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of lithol, / Propylene oxide modified hexa (meth) acrylate, 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. The melamine structure, benzoguanamine structure refers to a chemical structure having at least one triazine ring or phenyl-substituted triazine ring as a basic skeleton, and also includes 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, N, N, N-tetra (alkoxymethyl) glycoluril and the like.

Among these polyfunctional monomers, polyfunctional (meth) acrylates obtained by reacting a trifunctional or higher aliphatic polyhydroxy compound with (meth) acrylic acid, caprolactone modified polyfunctional (meth) acrylates, polyfunctional urethane (meth) (Meth) acrylate having a carboxyl group, N, N, N, N, N, N-hexa (alkoxymethyl) melamine and N, N, N, N-tetra (alkoxymethyl) benzoguanamine are preferable Do. 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, The strength of the colored layer is high and the surface smoothness of the colored layer is excellent and it is difficult to generate background contamination and film residue 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 from 10 to 1,000 parts by mass, particularly preferably from 20 to 500 parts by mass, per 100 parts by mass of the colorant (A). In this case, if the content of the polyfunctional monomer is too small, there is a fear that sufficient curability is not obtained. On the other hand, if the content of the polyfunctional monomer is too large, alkali developability is lowered when the alkali developing property is imparted to the coloring composition of the present invention, so that background contamination, film residue, etc. are formed on the substrate of the unexposed portion or on the light- It tends to be easier to do.

- (D) Binder Resin -

The coloring composition of the present invention may contain (D) a binder resin. Thus, the alkali developability of the coloring composition and the adhesion to the substrate can be enhanced. Such a binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as a &quot; carboxyl group-containing polymer &quot;) is preferable, and for example, an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter referred to as &quot; unsaturated monomer (d1) (Hereinafter referred to as &quot; unsaturated monomer (d2) &quot;).

Examples of the unsaturated monomer (d1) include unsaturated monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], omega-carboxypolycaprolactone mono , 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 maleimides such as N-phenylmaleimide and 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) (N = 2-10) methyl ether (meth) acrylate, polypropylene glycol (n = 2-10) methyl ether (meth) acrylate, polyethylene glycol Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8- (Meth) acrylate of glycidyl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (Meth) acrylate, 3,4-epoxycyclohexylmethyl ) Acrylate, 3 - [(meth) acryloyl-oxy-methyl] oxetane, 3- (meth) acrylic acid ester such as ethyl-3-oxetane [(meth) acryloyl-yloxymethyl];

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 Unexamined Patent Application Publication No. 5-19467, Japanese Unexamined Patent Application Publication No. 6-230212, Japanese Unexamined Patent Publication No. 7-207211, (Meth) acryloyl group and the like as a side chain, as disclosed in JP-A-09-325494, JP-A-11-140144 and JP-A-2008-181095 Containing polymer may be used as a binder resin.

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

The ratio (Mw '/ Mn') of the weight average molecular weight (Mw ') to the number average molecular weight (Mn') of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0 . Here, 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 produced by a known method, but for example, Japanese Unexamined Patent Application Publication No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871 The structure thereof, Mw, and Mw / Mn can be controlled by the method described above.

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, relative to 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 concentration of the colorant relatively decreases, There is a possibility that it becomes difficult to achieve the concentration.

- (E) Photopolymerization initiator -

(E) a photopolymerization initiator may be contained in the coloring composition of the present invention. Thus, 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 and X- .

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, an? -diketone compound, a polynuclear quinone compound, a diazo compound, and an imidosulfonate compound.

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.

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

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 non-imidazole-based compound is used as the 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 hydrogen donor and at least one amine hydrogen donor may further improve the sensitivity desirable.

Specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4, 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- [ 1- (9-ethyl-6- (2-methyl-4-tetrahydro-naphthalen- Yl) -, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- { Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -, 1- (O-acetyloxime).

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, particularly 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 too 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 (A) pigment in a solvent (F), a part of (B) a copolymer and, if necessary, (D) a binder resin, (E) a photopolymerization initiator, and (F) an additional (F) photopolymerization initiator, if necessary, to the pigment dispersion, ) Solvent, and the like, followed by mixing. As the solvent (F), any of the components (A) to (C) and other components constituting the coloring composition may be appropriately selected and used as long as they are dispersed or dissolved and reacted with these components and have 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) &quot;) is preferably used in combination.

Of these solvents, examples of the solvent (f1) include, for example,

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- -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) and the solvent (f2) contained in the colorant dispersion is preferably 0.5 / 99.5 to 40/60, more preferably 1/99 to 30/70, Particularly preferably 5/95 to 25/75.

Although the content of the solvent is not particularly limited, the amount is preferably such that the total concentration of each component except for the pigment dispersion or the coloring composition solvent is 5 to 50 mass%, preferably 10 to 20 mass% 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; A developing agent such as mono [2- (meth) acryloyloxyethyl succinic acid], phthalic acid mono [2- (meth) acryloyloxyethyl], omega -carboxylic polycaprolactone 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 of 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 where a pixel is formed, if necessary. Then, a liquid composition of a radiation-sensitive composition in which a red pigment is dispersed, for example, is coated on the substrate, and then the substrate is pre-baked to evaporate the solvent to form a coating film. Subsequently, this coating film is exposed through a photomask and then developed with an alkali developing solution 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 above-mentioned coloring and radiation-sensitive compositions is applied, prebaked, exposed, developed, and post-baked using each of the green and blue coloring and radiation-sensitive compositions to form a green pixel array and a blue pixel Arrays 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 can be formed by forming a metal thin film of chromium or the like formed by sputtering or vapor deposition into a desired pattern by photolithography. However, by using a coloring and radiation-sensitive composition in which a black pigment is dispersed, May be formed in the same manner as in the case of forming the gate electrode.

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

If desired, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition, or the like.

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 heat 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 a film thickness after drying, which is usually 0.6 to 8.0 탆, preferably 1.2 to 5.0 탆.

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 beam source such as an ion laser, a YAG laser, a XeCl excimer laser, or a nitrogen laser, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

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

Examples of the alkaline developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7- undecene, 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 development method, or 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 5.0 mu m, preferably 1.0 to 3.0 mu m.

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, first, a barrier wall having a light shielding function is formed on the surface of the substrate. Subsequently, the liquid composition of the coloring composition in which the red pigment is dispersed, for example, is discharged by the ink jet apparatus in the partition wall formed, and then the solvent is evaporated by pre-baking. Subsequently, this coating film is exposed, if necessary, and then cured by post-baking to form a red pixel pattern.

Subsequently, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate using each of the green or blue coloring compositions as described above. Thus, 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 partition wall has a thicker film than the black matrix used in the first method, because it has a function of preventing the coloring composition of each color discharged in the partition from being mixed, as well as the light shielding function. Therefore, the barrier rib is usually formed using a black radia radiation composition.

The substrate or radiation source used for forming the color filter, and the methods and conditions of prebaking and postbaking are the same as those of the first method. Thus, the 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 required, a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation sensitive composition, but it 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, but 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, the color filter may be formed on a substrate separate from the driving substrate on which the thin film transistor (TFT) is disposed, so that the substrate on which the driving substrate and the color filter are formed faces the 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 ITO (indium oxide doped with indium) electrode is formed face each other through a liquid crystal layer have. The latter structure can remarkably improve the aperture ratio and has an advantage that 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 the white LED include a white LED that obtains white light by using a red LED having an independent spectrum, a green LED and a blue LED, a white LED that obtains white light by mixing a red LED, a green LED, and a blue LED, A white LED that obtains white light by mixing LEDs with a red LED and a green phosphor, a white LED that obtains white light by mixing white light by combining a blue LED, a red light emitting phosphor, and a green light emitting phosphor, and a mixture of a blue LED and a YAG- A white LED for obtaining a white light by mixing a combination of an orange light emitting phosphor and a green light emitting phosphor, a combination of an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor and a blue light emitting phosphor by combining a white LED, White light emitting diode (LED), 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 take 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 take an appropriate structure and can take the structure disclosed in, for example, Japanese Patent Laid-Open No. 2007-41169.

[Example]

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

<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

EHMA: 2-ethylhexyl methacrylate

BzMA: Benzyl methacrylate

PME-200: Methoxypolyethylene glycol monomethacrylate (manufactured by Nichiyu Kagaku Co., Ltd.)

Synthesis Example 1

To the reaction vessel were added 600.30 g of THF, 10.80 g of lithium chloride (3.63 mass% concentration of THF solution) and 3.84 g of diphenylethylene, followed by cooling to -60 占 폚. Thereafter, 9.60 g (15.36 mass% concentration hexane solution) of n-butyllithium was added and aged for 10 minutes.

Next, a mixed solution of 103.84 g of nBMA and 13.45 g of EEMA was added dropwise over 30 minutes, and the reaction was continued for 15 minutes after dropwise addition. Then, gas chromatography (hereinafter referred to as GC) was measured to confirm disappearance of the monomer.

Next, 32.25 g of DMMA was added dropwise, and the reaction was continued for 30 minutes after dropwise addition. Then, the GC was measured and the disappearance of the monomer was confirmed. Then, 3.42 g of methanol was added to stop the reaction.

220 g of a propylene glycol monomethyl ether acetate solution having a concentration of 50 mass% of the obtained copolymer was heated to 160 캜 and aged for 3 hours. Thereafter, the solution was adjusted to a 40% by mass concentration of propylene glycol monomethyl ether acetate solution. 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 MA and nBMA was obtained. The obtained block copolymer is referred to as &quot; copolymer (B-1) &quot;.

Synthesis Example 2

To the reaction vessel were added 55.7 g of THF, 4.65 g of lithium chloride (4.54 mass% concentration of THF solution) and 0.45 g of diphenylethylene, and the mixture was cooled to -60 캜. Thereafter, 1.22 g (15.36 mass% concentration hexane solution) of n-butyllithium was added and aged for 10 minutes.

Next, a mixed solution of 1.66 g of EEMA, 9.9 g of nBMA, and 4.14 g of MMA was added dropwise over 120 minutes, and the reaction was continued for 15 minutes after dropwise addition. Then, the GC was measured to confirm disappearance of the monomer.

Next, 3.96 g of DMMA was added dropwise, and the reaction was continued for 30 minutes after dropwise addition. Then, the GC was measured and the disappearance of the monomer was confirmed. Then, 0.41 g of methanol was added to stop the reaction.

16.44 g of water was added to 65.64 g of a 25% by mass concentration propylene glycol monomethyl ether acetate solution of the obtained precursor polymer, and the mixture was heated to 100 占 폚 and reacted for 8 hours. The water was distilled off and adjusted to a 40% by mass concentration of propylene glycol monomethyl ether acetate solution. Thus, a block copolymer comprising an A block having a repeating unit derived from DAMA and a B block having repeating units derived from MA, nBMA and MMA was obtained. The obtained block copolymer is referred to as &quot; copolymer (B-2) &quot;.

Synthesis Example 3

In a flask equipped with a stirrer, 4.8 g of MA, 11.2 g of nBMA, 5.0 g of MMA, 302 mg of AIBN and 778 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 mL of toluene, And nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred, the temperature of the reaction solution was raised to 60 占 폚, and this temperature was maintained for 24 hours to perform living radical polymerization.

Subsequently, 364 mg of AIBN and 7.0 g of DAMA were dissolved in 20 mL 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 20 mass% solution of propylene glycol monomethyl ether 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 repeating units derived from MA, nBMA and MMA was obtained. The obtained block copolymer is referred to as &quot; copolymer (B-3) &quot;.

Synthesis Example 4

In a flask equipped with a stirrer, 3.4 g of MA, 2.2 g of nBMA, 14.0 g of MMA, 318 mg of AIBN and 821 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 mL of toluene, And nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred, the temperature of the reaction solution was raised to 60 DEG C, and the temperature was maintained for 24 hours to perform living radical polymerization.

Subsequently, 437 mg of AIBN and 8.4 g of DAMA were dissolved in 20 mL of toluene, and the solution was subjected to nitrogen substitution for 30 minutes. The resulting solution was subjected to living radical polymerization at 60 DEG C for 24 hours. Thereafter, the solution was adjusted to a 20 mass% solution of propylene glycol monomethyl ether acetate 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 repeating units derived from MA, nBMA and MMA was obtained. The obtained block copolymer is referred to as &quot; copolymer (B-4) &quot;.

Synthesis Example 5

In a flask equipped with a stirrer, 1.4 g of MA, 12.6 g of nBMA, 5.6 g of EHMA, 218 mg of AIBN and 561 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 mL of toluene, And nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred, the temperature of the reaction solution was raised to 60 DEG C, and the temperature was maintained for 24 hours to perform living radical polymerization.

Subsequently, 437 mg of AIBN and 8.4 g of DAMA were dissolved in 20 mL of toluene, and the solution was subjected to nitrogen substitution for 30 minutes. The resulting solution was subjected to living radical polymerization at 60 DEG C for 24 hours. Thereafter, the solution was adjusted to a 40 mass% solution of propylene glycol monomethyl ether acetate 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 repeating units derived from MA, PME-200, nBMA and EHMA was obtained. The obtained block copolymer is referred to as &quot; copolymer (B-5) &quot;.

Comparative Synthesis Example 1

To the reaction vessel, 568.08 g of THF, 11.56 g of lithium chloride (3.63 mass% concentration of THF solution) and 3.25 g of diphenylethylene were added and cooled to -60 占 폚. Thereafter, 7.16 g (15.36 mass% concentration hexane solution) of n-butyllithium was added and aged for 10 minutes.

Next, a mixed solution of 33.72 g of MMA, 15.52 g of nBMA, 13.14 g of BzMA, 15.79 g of EHMA and 11.94 g of PME-200 was added dropwise over 30 minutes, and the reaction was continued for 15 minutes after dropwise addition. GC was measured to confirm disappearance of the monomer.

Next, 30.09 g of DMMA was added dropwise, and the reaction was continued for 30 minutes after dropwise addition. Then, the GC was measured and the disappearance of the monomer was confirmed. Then, 2.52 g of methanol was added to stop the reaction. Thereafter, the solution was adjusted to a 40% by mass concentration of propylene glycol monomethyl ether acetate solution by vacuum distillation. Thus, a block copolymer comprising an A block having a repeating unit derived from DAMA and a B block having repeating units derived from MMA, PME-200, nBMA, BzMA and EHMA was obtained. The obtained block copolymer is referred to as &quot; copolymer (b-1) &quot;.

Comparative Synthesis Example 2

To the reaction vessel, 626.56 g of THF, 10.26 g of lithium chloride (3.63 mass% concentration of THF solution) and 3.23 g of diphenylethylene were added and cooled to -60 占 폚. Thereafter, 6.95 g (15.36 mass% concentration hexane solution) of n-butyllithium was added and aged for 10 minutes.

Next, a mixed solution of 26.52 g of MMA and 62.13 g of nBMA was added dropwise over 30 minutes, and the reaction was continued for 15 minutes after dropwise addition. Then, the GC was measured to confirm disappearance of the monomer.

Next, 42.19 g of DMMA was added dropwise, and the reaction was continued for 30 minutes after dropwise addition. Then, the GC was measured and the disappearance of the monomer was confirmed. Then, 3.79 parts of methanol was added to stop the reaction. Thereafter, the solution was adjusted to a 40% by mass concentration of propylene glycol monomethyl ether acetate solution by vacuum distillation. 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 MMA and nBMA was obtained. The obtained block copolymer is referred to as &quot; copolymer (b-2) &quot;.

Comparative Synthesis Example 3

In a flask equipped with a stirrer, 30 g of propylene glycol monomethyl ether acetate was charged and heated to 80 DEG C while nitrogen gas was introduced. At the same temperature, a solution prepared by dissolving 1.4 g of MA, 12.6 g of nBMA, 5.6 g of EHMA and 8.4 g of DAMA in 16 g of propylene glycol monomethyl ether acetate and 1.2 g of AIBN in 10 g of propylene glycol monomethyl ether acetate Was added dropwise over 2 hours at the same time. Thereafter, the temperature of the reaction solution was raised to 100 占 폚, and polymerization was carried out at this temperature for 1 hour. Thereafter, the solution was adjusted to a 40% by mass concentration of propylene glycol monomethyl ether acetate solution by vacuum distillation. Thus, a random copolymer of MA, nBMA, EHMA and DAMA was obtained. The obtained random copolymer is referred to as &quot; copolymer (b-3) &quot;.

<Measurement of Mw and Mw / Mn>

The Mw and Mn of the (B) copolymer obtained in each Synthesis Example were measured by GPC of the following specifications. The measurement results are shown in Table 1 as the copolymerization ratio (mass%) of each monomer in the copolymer (B).

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.

&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 divided into glass containers. After diluting with propylene glycol monomethyl ether acetate to 50 mL, phenolphthalein was added and titration was carried out with 0.1 N aqueous ethanolic potassium hydroxide solution to obtain a pink colored end point. A blank test was carried out in the same manner. 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 divided into glass containers. 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 additional 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 carried out in the same manner. (Unit: mgKOH / g) was calculated from the drop amount of 0.1 mol / L perchloric acid / acetic acid solution of the copolymer (B) in the blank test.

&Lt; Production of Pigment Dispersion >

Production Example 1

As a colorant, C.I. 9 parts by mass of Pigment Green 58 (manufactured by DIC), and 0.1 part by mass of C.I. 6 parts by mass of Pigment Yellow 150, 12.5 parts by mass of the copolymer (B-1) solution (nonvolatile component = 40% by mass), 64.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent and 8 parts by mass of propylene glycol monomethyl ether , And treated with a bead mill to prepare a pigment dispersion (A-1).

Production Examples 2 to 8 and Comparative Production Examples 1 to 7

(A-2) to (A-15) were prepared in the same manner as in Production Example 1 except that the kind and amount of the colorant, (B) the copolymer and the solvent were changed as shown in Table 2, ).

&Lt; Evaluation of Pigment Dispersion >

The viscosity of the resulting pigment dispersion was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The obtained colorant dispersion was filled in a light-shielding glass container and allowed to stand in a closed state at 23 占 폚 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; Pigment Green 58, and &quot; Y150 &quot; Pigment Yellow 150, and &quot; B15: 6 &quot; Pigment Blue 15: 6, &quot; V23 &quot; Pigment violet 23, and &quot; Y179 &quot; Solvent yellow 179, propylene glycol monomethyl ether acetate &quot; PGMEA &quot; and propylene glycol monomethyl ether &quot; PGME &quot;, respectively.

&Lt; Synthesis of binder resin >

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 44.0 g of p-vinylbenzyl glycidyl ether, 40.0 g of N-phenylmaleimide and 16.0 g of BzMA were dissolved in 300 g of propylene glycol monomethyl ether acetate, and 8.0 g of AIBN And 8.0 g of? -Methylstyrene dimer were charged, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 DEG C with stirring and nitrogen bubbling and polymerized for 5 hours.

Subsequently, 17.0 g of MA, 0.5 g of p-methoxyphenol and 4.4 g of tetrabutylammonium bromide were added to this reaction solution, and the reaction was carried out at 120 DEG C for 9 hours. Further, 18.5 g of succinic anhydride was added and the mixture was reacted at 100 ° C for 6 hours. Then, the mixture was washed twice with the liquid temperature maintained at 85 ° C and concentrated under reduced pressure to obtain 33% by mass of the binder resin (D- Was obtained. The binder resin (D-1) had a weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) = 7,800, a weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) The ratio of the average molecular weight was 2.8.

Synthesis Example 7

In a flask equipped with a cooling tube and a stirrer, 30.0 g of BzMA, 20.0 g of nBMA, 15.0 g of hydroxyethyl methacrylate, 20.0 g of styrene and 15.0 g of MA were dissolved in 200 g of propylene glycol monomethyl ether acetate, and further AIBN 3.0 g and? -Methylstyrene dimer 5.0 g were charged, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 캜 while stirring and nitrogen bubbling, and polymerized for 5 hours to obtain a solution containing 33% by mass of the binder resin (D-2). The binder resin (D-2) had a weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) = 10,000, a weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) The ratio of the average molecular weight was 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, And 14.0 g of hydroxyethyl methacrylate were dissolved in 300 g of propylene glycol monomethyl ether acetate. Further, 6.0 g of AIBN and 6.0 g of? -Methyl styrene dimer were added, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 DEG C while stirring and nitrogen bubbling, and polymerized for 5 hours to obtain a precursor copolymer solution.

To 200 g of the resulting 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. The reaction solution was rinsed twice with 75 g of ion-exchanged water per one time and concentrated under reduced pressure to obtain a solution containing 33 mass% of the binder resin (D-3). The binder resin (D-3) had a weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) = 11,000, a weight average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) Molecular weight ratio = 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), 31.5 parts by mass of the binder resin (D-2) solution as the binder resin, 10.4 parts by mass of M-402 (main component of dipentaerythritol hexaacrylate) manufactured by Toagosei Chemical Industry Co., , 4.3 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals Inc.) as a photopolymerization initiator, And 80.0 parts by mass of ethyl 3-ethoxypropionate were mixed to prepare a liquid color composition.

Evaluation of Missing Time

The obtained liquid composition was coated on a glass substrate using a spin coater and then prebaked on a hot plate at 100 캜 for 2 minutes to form a coating film having a thickness of 2.7 탆. Subsequently, after the substrate was cooled to room temperature, radiation including wavelengths of 365 nm, 405 nm, and 436 nm was irradiated onto the coating film on the substrate using a high-pressure mercury lamp at 1,000 J / m ² &lt; / RTI &gt; exposure dose. Thereafter, a shower phenomenon was carried out by discharging a 0.04 mass% aqueous potassium hydroxide solution at 23 캜 at a development pressure (nozzle diameter: 1 mm) of 1.0 kgf / cm ² to the coating film on the substrate. At this time, the time (missing time) until the coating film of the unexposed portion completely peeled off was measured. A &quot;,&quot; B &quot;,&quot; C &quot;, and &quot; D &quot; when the dropout time was less than 60 seconds was evaluated. The shorter this time, the faster the developing speed and the advantage that the tact time of the color filter manufacturing can be shortened. The evaluation results are shown in Table 3.

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 100 캜 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 irradiated with a high-pressure mercury lamp to irradiate each coating film with radiation having wavelengths of 365 nm, 405 nm, and 436 nm, / m &lt; ^{2 &} gt ;. Thereafter, post baking was performed at 220 캜 for 20 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 were measured at the C light source and at the 2-degree field, using the color analyzer (MCPD2000 manufactured by Otsuka Denshi Co., Ltd.) Respectively. From the measurement results, the chromaticity coordinate value x and the magnetic pole value (Y) at the chromaticity coordinate value y = 0.590 were obtained. The evaluation results are shown in Table 3.

Evaluation of contrast

The contrast was measured using a contrast meter (CT-1 manufactured by Tsubo Sakae Denkim Co., Ltd.) for the three cured films obtained in the &quot; Evaluation of Chrominance Characteristics &quot;. From the measurement results, the contrast at the chromaticity coordinate value y = 0.590 was obtained. The evaluation results are shown in Table 3.

Examples 2 to 8 and Comparative Examples 1 to 7

The preparation and evaluation of the colored composition were carried out in the same manner as in Example 1 except that the pigment dispersion, the binder resin, the crosslinking agent, the photopolymerization initiator and the solvent were changed as shown in Table 3 Respectively. The evaluation results are shown in Table 3. The chromaticity coordinate value x, the stimulus value Y and the contrast at the chromaticity coordinate value y = 0.090 were determined for the blue coloring composition (Example 8 and Comparative Examples 3 and 4). 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: M-402, manufactured by Toagosei Co., Ltd.)

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 OX02, Lt; / RTI &gt;

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 (18)

(A), (B) and (C);
(A) a colorant containing a pigment,
(1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group, wherein the repeating unit (1) (Mw / Mn) of from 1.0 to 1.9 and a copolymerization ratio of the repeating unit (2) to the sum of the weight average molecular weight Mw and the number average molecular weight Mn is 92.9 mass% to 99 mass%, and
(C) Crosslinking agent
And a coloring composition for a color filter.
&Lt; Formula 1 >

(1)
R ¹ represents a hydrogen atom or a methyl group,
Z represents -N ⁺ R ² R ³ R ⁴ Y ^- (wherein R ² to R ⁴ independently represent a hydrogen atom or a hydrocarbon group, and two or more of R ² to R ⁴ bond to each other to form a saturated heterocycle) Or Y ^- represents a counter anion), or -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group, and R ⁵ and R ⁶ are bonded to each other to form a saturated heterocyclic ring ), &Lt; / RTI >
X ¹ represents a divalent linking group]
(2)

(2)
R ⁷ represents a hydrogen atom or a methyl group,
And R &lt; ⁸ &gt; represents an aliphatic hydrocarbon group. delete The color filter according to claim 1, wherein the copolymer (B) is a block copolymer comprising an A block having the repeating unit (1) and a B block having the repeating unit (2) and the repeating unit (3) &Lt; / RTI &gt; The coloring composition for a color filter according to claim 1, wherein the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of the copolymer (B) is 1.0 to 1.7. The coloring composition for a color filter according to claim 1, further comprising (D) a binder resin (excluding the component (B)). The coloring composition for a color filter according to claim 1, further comprising (E) a photopolymerization initiator. The coloring composition for a color filter according to claim 1, further comprising a dye as a coloring agent. The coloring composition for a color filter according to claim 1, wherein the copolymerization ratio of the repeating unit (1) in the copolymer (B) is 5 to 70 mass% in the total repeating units. The coloring composition for a color filter according to claim 1, wherein the acid value of the copolymer (B) is 5 to 70 mgKOH / g. (A), (B) and (C);
(A) a colorant containing a pigment,
(1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group, wherein the repeating unit (1) Wherein the copolymerization ratio of the repeating unit (2) to the total of the repeating units (2) is 92.9 mass% to 99 mass%, the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is 1.0 to 1.9, 1) in the total repeating units is from 15 to 30% by mass, and
(C) Crosslinking agent
And a coloring composition for a color filter.
&Lt; Formula 1 >

(1)
R ¹ represents a hydrogen atom or a methyl group,
Z represents -N ⁺ R ² R ³ R ⁴ Y ^- (wherein R ² to R ⁴ independently represent a hydrogen atom or a hydrocarbon group, and two or more of R ² to R ⁴ bond to each other to form a saturated heterocycle) Or Y ^- represents a counter anion), or -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group, and R ⁵ and R ⁶ are bonded to each other to form a saturated heterocyclic ring ), &Lt; / RTI >
X ¹ represents a divalent linking group]
(2)

(2)
R ⁷ represents a hydrogen atom or a methyl group,
And R ⁸ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group] (A), (B) and (C);
(A) a colorant containing a pigment,
(1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group, wherein the repeating unit (1) (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is 1.0 to 1.9, and the content of the repeating units (2) and (2) is 75% Wherein the repeating unit (3) has no repeating unit (3) and contains the repeating unit (1) and the repeating unit (2) and the repeating unit (3) Block copolymer, and
(C) Crosslinking agent
And a coloring composition for a color filter.
&Lt; Formula 1 >

(1)
R ¹ represents a hydrogen atom or a methyl group,
Z represents -N ⁺ R ² R ³ R ⁴ Y ^- (wherein R ² to R ⁴ independently represent a hydrogen atom or a hydrocarbon group, and two or more of R ² to R ⁴ bond to each other to form a saturated heterocycle) Or Y ^- represents a counter anion), or -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group, and R ⁵ and R ⁶ are bonded to each other to form a saturated heterocyclic ring ), &Lt; / RTI >
X ¹ represents a divalent linking group]
(2)

(2)
R ⁷ represents a hydrogen atom or a methyl group,
And R ⁸ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group] A color filter comprising a coloring layer formed using the coloring composition for a color filter according to any one of claims 1 to 11. A display device comprising the color filter according to claim 12. The following components (a1), (B) and (F);
(a1) a pigment,
(1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group, wherein the repeating unit (1) (Mw / Mn) of from 1.0 to 1.9 and a copolymerization ratio of the repeating unit (2) to the sum of the weight average molecular weight Mw and the number average molecular weight Mn is 92.9 mass% to 99 mass%, and
(F) Solvent
And a pigment dispersed in the pigment dispersion.
&Lt; Formula 1 >

(1)
R ¹ represents a hydrogen atom or a methyl group,
Z represents -N ⁺ R ² R ³ R ⁴ Y ^- (wherein R ² to R ⁴ independently represent a hydrogen atom or a hydrocarbon group, and two or more of R ² to R ⁴ bond to each other to form a saturated heterocycle) Or Y ^- represents a counter anion), or -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group, and R ⁵ and R ⁶ are bonded to each other to form a saturated heterocyclic ring ), &Lt; / RTI >
X ¹ represents a divalent linking group]
(2)

(2)
R ⁷ represents a hydrogen atom or a methyl group,
And R &lt; ⁸ &gt; represents an aliphatic hydrocarbon group. The pigment dispersion for a color filter according to claim 14, wherein the copolymerization ratio of the repeating unit (1) in the copolymer (B) is 5 to 70 mass% in the total repeating units. The pigment dispersion for a color filter according to claim 14, wherein the (B) copolymer has an acid value of 5 to 70 mgKOH / g. The following components (a1), (B) and (F);
(a1) a pigment,
(1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group, wherein the repeating unit (1) Wherein the copolymerization ratio of the repeating unit (2) to the total of the repeating units (2) is 92.9 mass% to 99 mass%, the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is 1.0 to 1.9, 1) in the total repeating units is from 15 to 30% by mass, and
(F) Solvent
And a pigment dispersed in the pigment dispersion.
&Lt; Formula 1 >

(1)
R ¹ represents a hydrogen atom or a methyl group,
Z represents -N ⁺ R ² R ³ R ⁴ Y ^- (wherein R ² to R ⁴ independently represent a hydrogen atom or a hydrocarbon group, and two or more of R ² to R ⁴ bond to each other to form a saturated heterocycle) Or Y ^- represents a counter anion), or -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group, and R ⁵ and R ⁶ are bonded to each other to form a saturated heterocyclic ring ), &Lt; / RTI >
X ¹ represents a divalent linking group]
(2)

(2)
R ⁷ represents a hydrogen atom or a methyl group,
And R ⁸ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group] The following components (a1), (B) and (F);
(a1) a pigment,
(1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) having an acidic group, wherein the repeating unit (1) (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is 1.0 to 1.9, and the content of the repeating units (2) and (2) is 75% Wherein the repeating unit (3) has no repeating unit (3) and contains the repeating unit (1) and the repeating unit (2) and the repeating unit (3) Block copolymer, and
(F) Solvent
And a pigment dispersed in the pigment dispersion.
&Lt; Formula 1 >

(1)
R ¹ represents a hydrogen atom or a methyl group,
Z represents -N ⁺ R ² R ³ R ⁴ Y ^- (wherein R ² to R ⁴ independently represent a hydrogen atom or a hydrocarbon group, and two or more of R ² to R ⁴ bond to each other to form a saturated heterocycle) Or Y ^- represents a counter anion), or -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group, and R ⁵ and R ⁶ are bonded to each other to form a saturated heterocyclic ring ), &Lt; / RTI >
X ¹ represents a divalent linking group]
(2)

(2)
R ⁷ represents a hydrogen atom or a methyl group,
And R ⁸ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group]