KR20130026389A - Coloring composition for color filter, color filter and display device - Google Patents

Abstract

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

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

Description

Color composition, color filter, and display element for color filters {COLORING COMPOSITION FOR COLOR FILTER, COLOR FILTER AND DISPLAY DEVICE}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a coloring composition for color filters, a color filter, and a display element, and more particularly, to a color filter used for a transmissive or reflective color liquid crystal display element, a solid-state image sensor, an organic EL display element, an electronic paper, and the like. It relates to a color composition for a color filter used for formation of a colored layer, a color filter having a colored layer formed using the colored composition, and a display element comprising the color filter.

In manufacturing a color filter using a colored radiation sensitive composition, after apply | coating a pigment dispersion type colored radiation sensitive composition on a board | substrate and drying, a dry coating film is irradiated to a desired pattern shape (henceforth "exposure"). And the method (for example, patent documents 1-2) which obtain the pixel of each color by developing. Moreover, the method (for example, patent document 3) which forms a black matrix using the photopolymerizable composition which disperse | distributed carbon black is also known. Moreover, the method (for example, patent document 4) which obtains the pixel of each color by the inkjet system using the pigment dispersion type colored resin composition is also known.

By the way, in the field of the color filter used for a liquid crystal display element or a solid-state image sensor, the pigment used tends to become more and more atomized according to the request of high brightness and high contrast. It is known that it is effective to use a dispersant in order to realize stable and good dispersion of such atomized pigment. Various methods (for example, patent documents 5-6) are proposed which improve the dispersibility of a pigment using such a dispersing agent, and improve not only contrast, dispersion stability, but also developability.

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 Laid-Open No. 2003-26949 Japanese Patent Publication No. 2009-25813

However, also by the method described in these patent documents 5-6, it is difficult to realize the request of the high contrast, high color purity, and high brightness of the recent color liquid crystal display element. In particular, in the case of using a quinophthalone-based pigment represented by CI Pigment Yellow 138 as a coloring agent, the pigment dispersion solution prepared by the conventionally proposed dispersing method and known dispersant not only increases the viscosity but also deteriorates the storage stability. Therefore, it is difficult to endure practical use, and the color filter produced using the pigment dispersion solution has a problem such as insufficient contrast. For this reason, there is a strong demand for development of a color filter coloring composition that has recently realized the demand for high contrast, high color purity and high brightness, and is excellent in dispersibility and storage stability.

Therefore, the subject of this invention is providing the coloring composition for color filters which is excellent in chromaticity characteristics and excellent in dispersibility and storage stability using the quinophthalone type pigment represented by C.I. pigment yellow 138 as a coloring agent. Moreover, the subject of this invention is providing the color filter which comprises the colored layer formed from the said coloring composition, and the display element provided with this color filter.

In view of such a situation, the present inventors earnestly studied and found that the said subject could be solved by using the copolymer which has a specific repeating unit, and completed this invention.

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

(A) a colorant containing a quinophthalone pigment,

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

(C) crosslinking agent

It is providing the coloring composition for color filters containing containing.

In formula (1),

R ¹ represents a hydrogen atom or a methyl group,

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

X ¹ represents a divalent connector]

In Formula (2),

R ⁴ represents a hydrogen atom or a methyl group,

R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.]

Moreover, this invention provides the color filter which comprises the colored layer formed using the said coloring composition, and the display element provided with this color filter. Here, "colored layer" means each color pixel used for a color filter, a black matrix, a black spacer, etc.

In addition, the present invention provides the following components (a1), (B) and (F);

(a1) quinophthalone pigments,

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

(F) solvent

It is to provide a pigment dispersion for color filters, characterized in that it contains.

The coloring composition for color filters of this invention is excellent in chromaticity characteristics, and is excellent also in dispersibility and storage stability. By using the coloring composition of this invention, the color filter which has each color pixel with high contrast can be obtained.

Therefore, the coloring composition for color filters of this invention is used for manufacture of various color filters, including the color filter for color liquid crystal display elements, the color filter for color separation of a solid-state image sensor, the color filter for organic electroluminescent display elements, and the color filter for electronic paper. It can be used very preferably.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Color composition for color filters

Hereinafter, the structural component of the coloring composition for color filters (henceforth simply a "coloring composition") of this invention is demonstrated.

- (A) Colorant -

The coloring composition of this invention contains (a1) quinophthalone type pigment as a coloring agent, It is characterized by the above-mentioned.

As the quinophthalone pigment, C.I. Pigment Yellow 138 is preferable in view of the availability of raw materials and the absorption spectrum.

In the present invention, the (a1) quinophthalone pigments may be used alone or in combination of two or more thereof. Moreover, the coloring composition of this invention can contain (a2) another coloring agent further with (a1) quinophthalone type pigment as a coloring agent. It does not specifically limit as (a2) another coloring agent, For example, it can be set as the coloring composition for forming a green pixel by using (a1) quinophthalone type pigment with a green coloring agent. Moreover, it can be set as the coloring composition for forming a red pixel or a yellow pixel by using (a1) quinophthalone type pigment with a red coloring agent.

Although any of pigments, dyes, and natural pigments other than a quinophthalone pigment can be used as another coloring agent (a2), organic pigment and organic dye are preferable in the meaning of obtaining the pixel with high brightness and color purity. Examples of the organic pigment include compounds classified as pigments in the color index (C.I .; issued by The Society of Dyers and Colourists), that is, those having the following color index (C.I.) names.

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

CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment CI Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI pigment orange 73, CI pigment orange 74;

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

CI Pigment Brown 23, CI Pigment Brown 25;

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

Xanthene-based lake pigments described in Japanese Patent Laid-Open No. 2010-26334;

Rhodamine-based lake pigments described in Japanese Patent Laid-Open No. 2010-191304 and Japanese Patent Laid-Open No. 2011-22502;

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

Various lake pigments of Unexamined-Japanese-Patent No. 2010-237569, Unexamined-Japanese-Patent No. 2011-6602, and Unexamined-Japanese-Patent No. 2011-150195.

Examples of the organic dyes include those having the following color index (C.I.) names.

CI acid yellow 11, CI acid orange 7, CI acid red 37, CI acid red 180, CI acid blue 29, CI direct red 28, CI direct red 83, CI direct yellow 12, CI direct orange 26, CI direct green 28, CI direct green 59, CI reactive yellow 2, CI reactive red 17, CI reactive red 120, CI reactive black 5, CI disperse orange 5, CI disperse red 58, CI disperse blue 165, CI basic blue Azo dyes, such as 41, CI basic red 18, CI modular red 7, CI modular yellow 5, and CI modular black 7;

Anthraquinone dyes such as CI bat blue 4, CI acid blue 40, CI acid green 25, CI reactive blue 19, CI reactive blue 49, CI disperse red 60, CI disperse blue 56 and CI disperse blue 60 ;

Phthalocyanine-based dyes such as C.I. bat blue 5;

Quinoneimine dyes such as C.I. basic blue 3 and C.I. basic blue 9;

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

Nitro dyes such as C.I. acid yellow 1, C.I.acid orange 3, and C.I.disperse yellow 42;

Methine dyes such as Disperse Yellow 201.

In this invention, (a2) another coloring agent can be used individually or in mixture of 2 or more types.

In the present invention, the pigment may be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. Moreover, a pigment can also be used, modifying the particle surface with resin according to the objective. As resin which modifies the particle surface of a pigment, the vehicle resin of Unexamined-Japanese-Patent No. 2001-108817, or resin for disperse | distributing various pigments on the market are mentioned, for example. As a resin coating method of the carbon black surface, the method as described in Unexamined-Japanese-Patent No. 9-71733, Unexamined-Japanese-Patent No. 9-95625, Unexamined-Japanese-Patent No. 9-124969, etc. are mentioned, for example. Can be adopted. In addition, an organic pigment can also refine | miniaturize and use a primary particle by what is called salt milling. As a method of salt milling, the method disclosed by Unexamined-Japanese-Patent No. 08-179111 can be employ | adopted, for example.

When the coloring composition of this invention is used for formation of a green pixel, as (A) coloring agent, the group which consists of CI pigment green 7, CI pigment green 36, and CI pigment green 58 with (a1) quinophthalone type pigment It is preferable to contain at least 1 sort (s) chosen from. In this case, the content ratio of the (a1) quinophthalone pigment is preferably 1 to 80% by mass, more preferably 2 to 70% by mass, of CI pigment green 7, CI pigment green 36, and the total colorants. The total content ratio of at least one selected from the group consisting of CI pigment green 58 is preferably 20 to 99% by mass, more preferably 30 to 98% by mass in all the colorants.

(A) Since the content rate of a coloring agent forms a pixel with high brightness | luminance and excellent color purity, or a black matrix excellent in light-shielding property, it is 5-70 mass% in solid content of a coloring composition normally, Preferably it is 5-60 mass %to be. Solid content is components other than the solvent mentioned later here.

-(B) copolymer-

(B) copolymer in this invention is a copolymer which contains a repeating unit (1) and a repeating unit (2), and whose amine number is 80-250 mgKOH / g, and functions as a dispersing agent of (A) coloring agent.

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

In the said General formula (1), as R <^1> , a methyl group is preferable among a hydrogen atom and a methyl group.

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

The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, more specifically an alkyl group having 1 to 20 carbon atoms, further 1 to 12 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, C2-C20, Furthermore, 2-12 alkynyl group is mentioned. Specifically, as the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group , An octyl group, a decyl group, a dodecyl group, etc. are mentioned. As the alkenyl group, for example, an ethenyl group, 1-propenyl group, 1-butenyl group, 1,3-butadienyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-ethyl- 2-butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group, 2-decenyl group, etc. are mentioned, As an alkynyl group, for example, an ethynyl group, 1-propynyl group, 1 -Butynyl, 1-pentynyl, 3-pentynyl, 1-hexynyl, 2-ethyl-2-butynyl, 2-octynyl, (4-ethynyl) -5-hexynyl, 2-decynyl, etc. Can be mentioned.

Moreover, as said alicyclic hydrocarbon group, a C3-C20, Furthermore, 3-12 alicyclic hydrocarbon group is preferable, Specifically, a C3-C20, Furthermore, 3-12 cycloalkyl group is mentioned, More specifically, cyclo A propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, etc. are mentioned. Here, in this invention, the "alicyclic hydrocarbon group" is a general term of the thing except the aromatic compound among the carbocyclic compounds which have the structure which the carbon atom couple | bonded cyclically, and also includes having the above-mentioned aliphatic hydrocarbon group as a substituent or a linking group with -COO-. I shall do it.

Moreover, as said aromatic hydrocarbon group, C6-C20, Furthermore, 6-14, Furthermore, 6-10 aromatic hydrocarbon group is preferable, More specifically, C6-C20, Furthermore, 6-14, Furthermore, 6-10 Aryl group is mentioned. Can be. Here, in this invention, an "aryl group" means monocyclic to tricyclic aromatic hydrocarbon group, and a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, an azulenyl group, etc. are mentioned specifically ,.

Moreover, as a substituent of a hydrocarbon group, a halogen atom, a hydroxyl group, a C1-C6 alkoxy group, etc. are mentioned, for example. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, A pentyloxy group, a phenoxy group, etc. are mentioned.

In addition, in this invention, a "nitrogen-containing heterocyclic group" means the heterocyclic group which has at least 1 nitrogen atom as a component of a ring, and it is preferable that it is a heteromonocyclic group or a condensed heterocyclic group which these two condensate. These heterocyclic groups may be unsaturated rings or saturated rings, and may have a heteroatom (for example, an oxygen atom and a sulfur atom) other than a nitrogen atom in the ring.

As an unsaturated heterocycle, a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a triazole ring, an imidazoline ring, a piperazine ring, etc. are mentioned, for example. Moreover, as a saturated heterocycle, a morpholine ring, a piperidine ring, a tetrahydropyrimidine ring, etc. are mentioned, for example. Moreover, as a substituent in a nitrogen-containing heterocyclic group, a C1-C6 alkyl group, a halogen atom, a carboxyl group, an alkoxycarbonyl group, an alkoxy group, a hydroxyl group, an amino group, an amide group, a thiol group, a thioether group etc. are mentioned, for example. . Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, A bromine atom and an iodine atom are mentioned. As an alkoxycarbonyl group, a C2-C7 alkoxycarbonyl group is preferable, for example, A methoxycarbonyl group, an ethoxycarbonyl group, formyloxy group, an acetoxy group, benzoyloxy group etc. are mentioned specifically ,. As an alkoxy group, a C1-C6 alkoxy group is preferable, A methoxy group, an ethoxy group, a propoxy group, isopropoxy group, butoxy group, a pentyloxy group, a phenoxy group etc. are mentioned specifically ,. As an amino group, an amino group, a methylamino group, a diethylamino group, a diphenylamino group, etc. are mentioned, for example, A formamide group, an acetamide group, a propioamide group, etc. are mentioned as an amide group. As a thioether group, a C1-C6 thioether group is preferable, A methylthioether group, an ethylthioether group, a butylthioether group etc. are mentioned specifically ,.

As said hetero monocyclic group, a 5-7 membered ring is preferable, Specifically, the group which has a basic skeleton represented by following General formula (1-1) is mentioned, These hetero monocyclic groups may have a substituent.

In general formula (1-1), "*" represents a bond.

Moreover, as said condensed heterocyclic group, the group which has a basic skeleton represented by following General formula (1-2)-(1-4) is mentioned specifically, These condensed heterocyclic group may have a substituent.

In the formulas (1-2) to (1-4), "*" represents a bond.

In the above formula (1), examples of the divalent linking group (X ¹ ) include an alkanediyl group having 1 to 10 carbon atoms and further 1 to 6 carbon atoms; An arylene group having 6 to 20 carbon atoms, further 6 to 14 carbon atoms; -CONH-R ¹⁰ -group; -COO-R ¹¹ -group etc. are mentioned. R ¹⁰ and R ¹¹ are each independently a single bond, an alkanediyl group having 1 to 10 carbon atoms, further 1 to 6 carbon atoms, or an alkyleneoxyalkylene group having 2 to 10 carbon atoms. As the alkanediyl group, for example, methylene group, ethylene group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, Propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl group, pentane-1,5 -Diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, etc. are mentioned. Moreover, as an arylene group, a phenylene group, a naphthylene group, a biphenylene group, an anthylene group, etc. are mentioned, for example. Examples of the alkyleneoxyalkylene group having 2 to 10 carbon atoms include ethyleneoxyethylene group, ethyleneoxypropylene group, propyleneoxypropylene group, ethyleneoxybutylene group and the like.

Especially, as X <^1>, -COO-R <^11> -group is preferable and as R <^11> , a C2-C6 alkanediyl group is preferable.

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

In the said General formula (2), as R <^4> , a methyl group is preferable among a hydrogen atom and a methyl group.

As an aliphatic hydrocarbon group in R <^5> , an alkyl group, an alkenyl group, an alkynyl group, etc. are mentioned, for example. The aliphatic hydrocarbon group may be in any of linear and branched forms, and when the aliphatic hydrocarbon group is an alkenyl group or an alkynyl group, the position of the unsaturated bond may be either in the molecular chain or the terminal of the molecular chain.

Moreover, as an alicyclic hydrocarbon group in R <^5> , a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a temporary exchange hydrocarbon group, a spiro hydrocarbon group, a cyclic terpene hydrocarbon group, etc. are mentioned, for example. The alicyclic hydrocarbon group may further have a substituent, and examples of such substituents include a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and the like. Specific examples of these substituents include those similar to those described above.

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

(B) A copolymer may have a repeating unit of that excepting the above, As an example of such a repeating unit, the repeating unit represented by following General formula (3) (henceforth "repeating unit (3)"); Repeating units having an acidic group (hereinafter also referred to as "repeating unit (4)"); Styrene-based monomers such as styrene and? -Methylstyrene; (Meth) acrylic-acid aralkyl esters, such as benzyl (meth) acrylate; Quaternary ammonium salt structures such as (meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium chloride, and (meth) acryloyloxyethylbenzyldiethylammonium chloride (Meth) acrylic acid ester having; (Meth) acrylic acid halide monomers such as (meth) acrylic acid chloride; (Meth) acrylamide monomers, such as (meth) acrylamide and N-methylol acrylamide; Vinyl acetate; Acrylonitrile; Allyl glycidyl ether; Crotonic acid glycidyl ether; And repeating units derived from monomers such as N-methacryloyl morpholine. Especially, it is preferable to have at least any one of a repeating unit (3) and a repeating unit (4) from a dispersible viewpoint, and it is more preferable to have a repeating unit (3). Here, in this invention, "(meth) acrylate" shall mean "acrylate or methacrylate."

In formula (3),

R ⁶ represents a hydrogen atom or a methyl group,

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

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

n represents an integer of 1 to 150;

In general formula (3), as R <^6> , a methyl group among a hydrogen atom or a methyl group is preferable.

Moreover, as an alkanediyl group in R <^7> , an ethylene group, an ethane- 1, 1- diyl group, a propane- 1, 1- diyl group, a propane- 1, 2- diyl group, a propane- 1, 3- is mentioned, for example. Diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and the like.

Examples of the alkyl group in R ⁸ include the same groups as described above.

Although n represents the integer of 1-150, the integer of 1-20 is preferable, the integer of 1-10 is more preferable, the integer of 1-5 is especially preferable.

The repeating unit (4) is gatneunde an acidic group, such as the acidic group is not particularly limited, for example, include a phenolic hydroxyl group, a carboxyl group, a sulfo _{group, -SO 2 NH 2, -C (} CF 3) 2 -OH , etc. Can be. In this invention, as an acidic group, a phenolic hydroxyl group and a carboxyl group are preferable at a point of dispersibility and alkali developability of the coloring composition obtained, and a carboxyl group is especially preferable.

As a repeating unit (4), the repeating unit represented by following General formula (4) is mentioned, for example.

In formula (4),

R ⁹ represents a hydrogen atom or a methyl group,

A represents an acidic group,

X ² represents a single bond or a divalent linking group]

In the said General formula (4), as R <^9> , a methyl group is preferable among a hydrogen atom and a methyl group.

Examples of the divalent linking group (X ² ) include an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 1 to 6 carbon atoms, an arylene group, a -CONH-R ¹² -group, a -COO-R ¹³ -group, and a -OCOR ¹⁴ -group. , -R ¹⁵ -OCO-R ^16- , -COO- (C _m H _2m COO) ₁ -C _m H _2m -group, -COO-R ¹⁷ -OCO-R ¹⁸ -and the like. Here, R ¹² to R ¹⁶ independently represent a single bond, an alkanediyl group having 1 to 10 carbon atoms, further 1 to 6 carbon atoms, or an alkyleneoxyalkylene group having 2 to 10 carbon atoms, and m represents an integer of 1 to 10. L represents an integer of 1 to 4, R ¹⁷ represents an alkanediyl group having 1 to 10 carbon atoms, further 1 to 6 carbon atoms, and R ¹⁸ represents a single bond, an alkanediyl group of 1 to 10 carbon atoms, further 1 to 6 carbon atoms. And a cyclohexane-1,2-diyl group or a phenylene group (eg, 1,2-phenylene group, 1,4-phenylene group). Specific examples of the alkanediyl group, arylene group, and alkyleneoxyalkylene group include those similar to those described above.

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

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

(i) When (B) copolymer consists only of repeating unit (1) and repeating unit (2), the copolymerization ratio of repeating unit (1) becomes like this. Preferably it is 20-80 mass% of all the repeating units, More preferably, It is 30-70 mass%, More preferably, it is 40-60 mass%, and the copolymerization ratio of a repeating unit (2) is remainder.

(ii) When the (B) copolymer has a repeating unit (1) and a repeating unit (3) other than the repeating unit (2), the copolymerization ratio of the repeating unit (1) is preferably 20 to 70 of all the repeating units. It is mass%, More preferably, it is 30-65 mass%, More preferably, it is 40-60 mass%, The copolymerization ratio of a repeating unit (2) becomes like this. Preferably it is 5-50 mass% of all the repeating units, More preferably, It is 10-45 mass%, More preferably, it is 15-40 mass%, The copolymerization ratio of a repeating unit (3) becomes like this. Preferably it is 5-40 mass%, More preferably, it is 10-30 mass% of all repeating units.

(iii) When the (B) copolymer has a repeating unit (3) and a repeating unit (4) other than the repeating unit (1) and the repeating unit (2), the copolymerization ratio of the repeating unit (1) is one of the total repeating units. Preferably it is 20-70 mass%, Furthermore, it is 30-65 mass%, Furthermore, it is 40-60 mass%, The copolymerization ratio of a repeating unit (2) becomes like this. Preferably it is 5-50 mass% of all the repeating units, More preferably, It is 10-45 mass%, More preferably, it is 15-40 mass%, The copolymerization ratio of a repeating unit (3) becomes like this. Preferably it is 5-40 mass%, More preferably, it is 10-30 mass%, The copolymerization ratio of the repeating unit (4) is preferably 1 to 10% by mass, more preferably 1 to 5% by mass of all the repeating units.

Although the amine number of (B) copolymer is 80 mgKOH / g or more and 250 mgKOH / g or less, from a viewpoint of further contrast improvement, Preferably it is 100-250 mgKOH / g, More preferably, it is 150-250 mgKOH / g, More preferably, it is 150-250 200 mgKOH / g, particularly preferably 155 to 190 mgKOH / g. Here, in this invention, an "amine value" is the mg number of the acid and equivalent KOH which are required to neutralize 1 g of non volatile matters from which the solvent of the copolymer solution was removed, and what is measured by the method as described in the Example mentioned later specifically Say.

On the other hand, when (B) copolymer has a repeating unit (4), the acid value of (B) copolymer becomes like this. Preferably it is 30 mgKOH / g or less, More preferably, it is 25 mgKOH / g or less, More preferably Is 20 mgKOH / g or less. Although a minimum in particular is not specifically limited, 0.5 mgKOH / g or more is preferable and 1 mgKOH / g or more is more preferable. Here, in this invention, an "acid value" is the mg number of KOH which is required to neutralize 1 g of non volatile matters from which the solvent of the copolymer solution was removed, and it means what is measured by the method as described in the Example mentioned later specifically.

The copolymer (B) is not particularly limited as long as it has a repeating unit (1) and a repeating unit (2), but in view of further improving dispersibility, the repeating unit (2), the repeating unit (3) and the repeating unit (4 A block having a repeating unit (1) without a), a repeating unit (2) and a repeating unit (3) without a repeating unit (1), and a B block having a repeating unit (4) depending on the purpose It is preferable that it is a block copolymer. It is preferable that the said block copolymer is an A-B block copolymer or a B-A-B block copolymer.

In A block, 2 or more types of repeating units (1) may be contained in one A block, and each repeating unit may be contained in any aspect of random copolymerization and block copolymerization in the said A block in that case. .

Moreover, repeating units other than a repeating unit (1) may be contained in A block, and the repeating unit derived from the (meth) acrylic acid ester which has the said quaternary ammonium salt structure as an example of such a repeating unit is mentioned.

In addition, in B block, the repeating unit (2), the repeating unit (3), and the repeating unit (4) may be contained in either aspect of random copolymerization and block copolymerization. (B) When the copolymer is a BAB block copolymer, a B1 block having a repeating unit (2) and a repeating unit (3) and no repeating unit (4), and a repeating unit (2) and a repeating unit (4) It may be a B1-A-B2 block copolymer having a B2 block having, but not having a repeating unit (3). In addition, the repeating unit (2), the repeating unit (3), and the repeating unit (4) may each contain two or more kinds in one B block, in which case each repeating unit is random copolymerized in the B block. And block copolymerization.

(B) copolymer can be manufactured by a well-known method, and when (B) copolymer is a block copolymer, it can be manufactured, for example by living-polymerizing the monomer which introduce | transduces each said repeating unit. As a living polymerization method, For example, Unexamined-Japanese-Patent No. 9-62002; Japanese Patent Laid-Open No. 2002-31713; See P. Lutz, P. Mason et al, Polym. Bull. 12, 79 (1984); B.C. Anderson, G.D. Andrews et al, Macromolecules, 14, 1601 (1981); See K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985); See K. Hatada, K. Ute, et al, Polym. J. 18, 1037 (1986); See Kote Koichi, Koda Kodai, Polymer Processing, 36, 366 (1987); Higashimura Toshinobu, Mitsuo Sawamoto, Polymer Society, 46, 189 (1989); See M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987); See Ida Dakuzo, 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. Part A Polym. Chem., 47, 3544-3557 (2009) and the like can be employed.

As a monomer which provides the repeating unit (1), for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acryl The rate etc. are mentioned. These can be used individually or in mixture of 2 or more types.

As a monomer which provides a repeating unit (2), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (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, tricyclopentenyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

As a monomer which provides the repeating unit (3), for example, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxypropylene glycol (Meth) acrylate, methoxy dipropylene glycol (meth) acrylate, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

Moreover, as a monomer which provides a repeating unit (4), for example, (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, (meth) acrylic acid carboxymethyl ester, (meth) acrylic acid 2-carboxylate Ethyl ester, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylbenzoic acid, p-hydroxystyrene, p-hydroxy-α- Methylstyrene, 2-acryloyloxyethylsulfonic acid, 2-methacryloxyethylsulfonic acid, sodium 2-acryloyloxyethylsulfonic acid, 2-acryloyloxyethylsulfonic acid lithium, 2-acryloyloxyethylsulfonic acid ammonium, 2-acryloyloxyethyl sulfonate imidazolium, 2-acryloyloxyethyl sulfonate pyridinium, sodium 2-methacryloxyethyl sulfonate, lithium 2-methacryloxyethyl sulfonate, ammonium 2-methacryloxyethyl sulfonate, 2-methacryloxyethylsulfonic acid imidazolium, 2-meta Krilloxy ethyl sulfonate pyridinium, styrene sulfonic acid, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

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

Further, the ratio (Mw / Mn) of Mw of the (B) block copolymer and Mn in terms of methyl methacrylate in terms of GPC (elution solvent: DMF) is preferably 1.0 to 1.9, more preferably 1.0 To 1.8, more preferably 1.0 to 1.7, more preferably 1.0 to 1.5, and particularly preferably 1.0 to 1.3. By making (B) a copolymer into such an aspect, the coloring composition excellent in dispersibility and alkali developability can be obtained.

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

In this invention, in order to improve dispersibility, you may further contain a well-known dispersing agent. Known dispersants include, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, and polyester series. Dispersing agents, acrylic dispersing agents, pigment derivatives, etc. are mentioned.

Such dispersants are commercially available, for example, as an acrylic dispersant, such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, manufactured by BYK), and urethane dispersants Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by Vicchemy), Solspers 76500 (manufactured by Lubrizol Co., Ltd.), sol as a polyethyleneimine-based dispersant Spurs 24000 (manufactured by Lubrizol Co., Ltd.) and polyester dispersant include Azisper PB821, Azisper PB822, Azisper PB880, and Azisper PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.). Moreover, as a specific example of a pigment derivative, copper phthalocyanine, diketopyrrolopyrrole, the sulfonic acid derivative of quinophthalone, etc. are mentioned.

-(C) crosslinking agent-

In the present invention, (C) crosslinking agent refers to a compound having two or more polymerizable groups. As a group which can superpose | polymerize, an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, an N-alkoxy methylamino group, etc. are mentioned, for example. In the present invention, as the (C) crosslinking agent, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

As a specific example of the said compound which has two or more (meth) acryloyl groups, the polyfunctional (meth) acrylate obtained by making an aliphatic polyhydroxy compound and (meth) acrylic acid react, and the polyfunctional (meth) acrylate modified with caprolactone , Polyfunctional urethane (meth) acrylate obtained by reacting alkylene oxide-modified polyfunctional (meth) acrylate, (meth) acrylate having hydroxyl group and polyfunctional isocyanate, (meth) acrylate having hydroxyl group and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making it react, etc. are mentioned.

Here, as the aliphatic polyhydroxy compound, for example, divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and The same trivalent or more aliphatic polyhydroxy compound is mentioned. As (meth) acrylate which has the said hydroxyl group, 2-hydroxyethyl (meth) acrylate, trimethylol propanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta, for example (Meth) acrylate, glycerol dimethacrylate, etc. are mentioned. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, etc. are mentioned, for example. As the acid anhydride, for example, anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydro phthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic dianhydride And tetrabasic dianhydrides such as benzophenone tetracarboxylic dianhydride.

Moreover, as said caprolactone modified polyfunctional (meth) acrylate, the compound described in Paragraph [0015]-[0018] of Unexamined-Japanese-Patent No. 11-44955 is mentioned, for example. Examples of the alkylene oxide-modified polyfunctional (meth) acrylates include di (meth) acrylates modified with at least one selected from ethylene oxide of bisphenol A and propylene oxide of bisphenol A, and ethylene oxide of isocyanuric acid. And a tree modified by at least one selected from tri (meth) acrylates selected from propylene oxide of isocyanuric acid, ethylene oxide of trimethylolpropane and propylene oxide of trimethylolpropane ( Tri (meth) acrylate modified by at least one selected from meth) acrylate, ethylene oxide of pentaerythritol and propylene oxide of pentaerythritol, ethylene oxide of pentaerythritol and propylene oxide of pentaerythritol Denatured by at least one Penta (meth) acrylate modified by at least one selected from tetra (meth) acrylate, ethylene oxide of dipentaerythritol and propylene oxide of dipentaerythritol, ethylene oxide and dipentaerythrate of dipentaerythritol Hexa (meth) acrylate etc. modified by at least 1 sort (s) chosen from the propylene oxide of a lititol are mentioned.

Moreover, as a compound which has the said 2 or more N-alkoxy methylamino group, the compound etc. which have a melamine structure, a benzoguanamine structure, a urea structure are mentioned, for example. In addition, a melamine structure and a benzoguanamine structure mean the chemical structure which has one or more triazine ring or a phenyl substituted triazine ring as a basic skeleton, and is a concept including melamine, benzoguanamine, or their condensate. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N '', N ''-hexa (alkoxymethyl) melamine, N, N, N ', N'-tetra (Alkoxymethyl) benzoguanamine, N, N, N ', N'- tetra (alkoxymethyl) glycoluril, etc. are mentioned.

Among these crosslinking agents, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, a caprolactone modified polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate, and a carboxyl group Polyfunctional (meth) acrylate having N, N, N ', N', N '', N ''-hexa (alkoxymethyl) melamine, N, N, N ', N'-tetra (alkoxymethyl) Benzoguanamine is preferred. In the polyfunctional (meth) acrylate obtained by making a trivalent or more aliphatic polyhydroxy compound and (meth) acrylic acid react, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipenta In the polyfunctional (meth) acrylate which erythritol hexaacrylate has a carboxyl group, the compound obtained by making pentaerythritol triacrylate and succinic anhydride react, and the compound obtained by making dipentaerythritol pentaacrylate and succinic anhydride react It is especially preferable at the point that the intensity | strength of a colored layer is high, the surface smoothness of a colored layer is excellent, and background contamination, a film | membrane residue, etc. are hard to produce on the board | substrate and the light shielding layer of an unexposed part.

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

10-1,000 mass parts is preferable with respect to 100 mass parts of (A) coloring agents, and, as for content of (C) crosslinking agent in this invention, 20-500 mass parts is especially preferable. In this case, when there is too little content of a crosslinking agent, there exists a possibility that sufficient sclerosis | hardenability may not be obtained. On the other hand, when there is too much content of a crosslinking agent, when alkali developability is provided to the coloring composition of this invention, alkali developability will fall and it will be easy to produce background contamination, a film residue, etc. on the board | substrate or light-shielding layer of an unexposed part. Tend to lose.

(D) Binder Resin-

The coloring composition of this invention can be made to contain (D) binder resin (except the said (B) component). Thereby, alkali developability and binding property to a board | substrate can be improved to a coloring composition. Although it does not specifically limit as such binder resin, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Especially, the polymer which has a carboxyl group (henceforth a "carboxyl group-containing polymer") is preferable, for example, copolymerization different from the ethylenically unsaturated monomer which has one or more carboxyl groups (henceforth "unsaturated monomer (d1)"). The copolymer of possible ethylenically unsaturated monomer (henceforth "unsaturated monomer (d2)") is mentioned.

Examples of the unsaturated monomer (d1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) acrylate. and p-vinyl benzoic acid.

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

Moreover, as said unsaturated monomer (d2), for example

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

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate , Polyethylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, poly Propylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) Ethylene oxide modified (meth) acrylate of acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, paracumylphenol, glycidyl (meth ) Acrylate, 3,4- (Meth) acrylic acid esters such as foxycyclohexylmethyl (meth) acrylate, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane ;

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) can be used individually or in mixture of 2 or more types.

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

As a specific example of the copolymer of an unsaturated monomer (d1) and an unsaturated monomer (d2), For example, Unexamined-Japanese-Patent No. 7-140654, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open No. 10-300922 Japanese Patent Laid-Open No. 11-174224 Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118 The copolymer disclosed in Unexamined-Japanese-Patent No. 2004-101728, etc. are mentioned.

In addition, in this invention, for example, Unexamined-Japanese-Patent No. 5-19467, Unexamined-Japanese-Patent No. 6-230212, Unexamined-Japanese-Patent No. 7-207211, Unexamined-Japanese-Patent ( As disclosed in Japanese Patent Application Laid-Open No. 09-325494, Japanese Patent Application Laid-Open No. 11-140144, Japanese Patent Application Laid-Open No. 2008-181095, and the like, a polymerizable unsaturated bond such as a (meth) acryloyl group in its side chain is disclosed. The carboxyl group-containing polymer which has a can also be used as binder resin.

The binder resin in this invention has the weight average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran) normally 1,000-100,000, Preferably it is 3,000-50,000. If Mw is too small, the remaining film ratio or the like of the resulting film may be lowered, the pattern shape, heat resistance, or the like may be impaired, or the electrical characteristics may be deteriorated, while if the Mw is too large, the resolution may be lowered or the pattern shape may be damaged, Moreover, there exists a possibility that a dry foreign material may become easy at the time of application | coating by a slit nozzle system.

Moreover, ratio (Mw '/ Mn') of the weight average molecular weight (Mw ') and number average molecular weight (Mw') of binder resin in this invention becomes like this. Preferably it is 1.0-5.0, More preferably, it is 1.0-3.0. In addition, Mw 'and Mn' said here mean the weight average molecular weight and number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

Binder resin in this invention can be manufactured by a well-known method, For example, it is disclosed by Unexamined-Japanese-Patent No. 2003-222717, 2006-259680, International Publication 07/029871, etc. The structure, Mw and Mw / Mn can also be controlled by the established method.

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

In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. When there is too little content of binder resin, alkali developability may fall, for example, there exists a possibility that the storage stability of the coloring composition obtained may fall, and when too much, since a coloring agent density | concentration falls relatively, it is aimed as a thin film. There is a fear that it is difficult to achieve the color density.

-(E) photoinitiator-

The coloring composition of this invention can be made to contain (E) photoinitiator. Thereby, the coloring composition can be imparted with radiation sensitivity. The (E) photoinitiator used for this invention is a compound which generate | occur | produces the active species which can start superposition | polymerization of said (C) crosslinking agent by exposure of radiation, such as visible light, an ultraviolet-ray, an ultraviolet-ray, an electron beam, X-rays.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -Diketone compounds, polynuclear quinone compounds, diazo compounds, imidosulfonate compounds, and the like.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. As a photoinitiator, at least 1 sort (s) chosen from the group of a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, and an O-acyl oxime type compound is preferable.

As a specific example of a thioxanthone type compound among the preferable photoinitiators in this invention, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- dichloro thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, etc. are mentioned.

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

Further, specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole etc. are mentioned.

Moreover, when using a biimidazole type compound as a photoinitiator, using a hydrogen donor together is preferable at the point which can improve a 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, and 4,4'-bis (di Amine hydrogen donors, such as ethylamino) benzophenone, are mentioned. In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof, but the combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors may further improve the sensitivity. Preferred at

In addition, specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4 Triazine type compounds which have halomethyl groups, such as a 6-bis (trichloromethyl) -s-triazine, are mentioned.

In addition, specific examples of the O-acyl oxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydro Furanylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2- Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. As a commercial item of an O-acyl oxime type compound, NCI-831, NCI-930 (above, the product made from Adeka Corporation) etc. can also be used.

In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. As such a sensitizer, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylamino acetophenone, 4-dimethylamino propiophenone, for example. Ethyl 4-dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl ) Coumarin, 4- (diethylamino) chalcone, and the like.

In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, when there is too little content of a photoinitiator, there exists a possibility that hardening by exposure may become inadequate, and when too large, there exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development.

-(F) solvent-

The coloring composition of this invention is a coloring agent containing the (a1) quinophthalone type pigment normally with the (B) copolymer and some other dispersing agents and (D) binder resin as needed in a (F) solvent, for example, For example, the mixture is dispersed and dispersed while grinding using a bead mill, a roll mill, or the like to form a pigment dispersion, and then (C) a crosslinking agent and, if necessary, (D) a binder resin, (E) a photopolymerization initiator, and further (F) It is manufactured by the method of adding and mixing a solvent and the like. As the solvent (F), the components (A) to (C) and other components constituting the coloring composition may be appropriately selected and used as long as they do not react with these components while dispersing or dissolving them. However, when manufacturing the said pigment dispersion liquid, the solvent which has a (f1) hydroxyl group from the point of dispersibility and stability (henceforth a "solvent (f1)"), and the solvent which does not have a (f2) hydroxyl group (henceforth " Also referred to as "solvent (f2)".

Of these solvents, for example, the solvent (f1)

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;

Keto alcohols, such as diacetone alcohol, etc. are mentioned.

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

As the solvent (f2), for example,

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (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;

Alkoxy carboxyl, such as 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl ethoxy acetate, and 3-methyl-3- methoxy butyl propionate Acid esters;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate Other esters such as 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, N-methylpyrrolidone and the like.

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 and propylene glycol monomethyl are particularly preferred. Ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 1,3-butylene glycol di Acetate, 1,6-hexanediol diacetate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate are preferred. Solvent (f2) can be used individually or in mixture of 2 or more types.

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

Although content of a solvent is not specifically limited, Regardless of whether it is a pigment dispersion liquid or a coloring composition, the quantity by which the total concentration of each component which removed the solvent of the said pigment dispersion liquid or a coloring composition becomes 5-50 mass% is preferable, Especially 10 It is preferable that the amount will be from 40% by mass. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability, and the coloring composition with favorable applicability | paintability and stability can be obtained.

-additive-

The coloring composition of this invention may contain various additives as needed.

As an additive, For example, fillers, such as glass and an alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as fluorine-based surfactants and silicone-based surfactants; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Adhesion promoter; 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; Developability improvement agents, such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], (omega) -carboxypolycaprolactone mono (meth) acrylate, etc. are mentioned. Can be.

Color filter and its manufacturing method

The color filter of this invention is equipped with the colored layer formed using the coloring composition of this invention.

As a method of manufacturing a color filter, the following method is mentioned first. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to partition a portion for forming a pixel as necessary. Subsequently, after apply | coating the liquid composition of the radiation sensitive composition of this invention in which the red coloring agent containing a quinophthalone type pigment was disperse | distributed on this board | substrate, prebaking is performed and a solvent is evaporated and a coating film is formed. . Subsequently, after exposing through a photomask to this coating film, it develops using alkaline developing solution, and removes and removes the unexposed part of a coating film. Thereafter, post-baking forms a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

Subsequently, using each green or blue colored radiation-sensitive composition, coating, prebaking, exposure, development and post-baking of each colored radiation-sensitive composition are carried out in the same manner as described above to obtain a green pixel array and a blue pixel array. Formed sequentially on the same substrate. As a result, 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 sputtering or depositing a metal thin film such as chromium formed by vapor deposition into a desired pattern using a photolithography method. However, the pixel formation is performed using a colored radiation-sensitive composition in which black pigment is dispersed. It may be formed in the same manner as in the case.

As a board | substrate used when forming a color filter, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example.

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

When the colored radiation-sensitive composition is applied to the substrate, appropriate coating methods such as spraying, roll coating, spin coating (spin coating), slit die coating, and bar coating can be employed. It is preferable to employ | adopt the slit die coating method.

Prebaking is normally performed combining a 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.

Coating thickness is 0.6-8 micrometers normally as a film thickness after drying, Preferably it is 1.2-5 micrometers.

As a light source of radiation used when forming a pixel and / or a black matrix, for example, xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, argon lamp etc. Laser light sources, such as an ion laser, a YAG laser, XeCl excimer laser, and a nitrogen laser, etc. are mentioned. Ultraviolet LED can also be used as an exposure light source. Preferably, the wavelength is in the range of 190 to 450 nm.

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

As the alkaline developer, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, Aqueous solutions, such as 1, 5- diazabicyclo- [4.3.0] -5-nonene, 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 developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid buildup) developing method, and the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

Post-baking conditions are about 10 to 60 minutes at 180-280 degreeC normally.

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

As a second method of manufacturing the color filter, a method of obtaining pixels of each color by an inkjet method disclosed in Japanese Patent Laid-Open No. 7-318723, Japanese Patent Laid-Open No. 2000-310706, or the like is adopted. can do. In this method, a partition which also serves as a light shielding function is first formed on the surface of the substrate. Subsequently, after discharging the liquid composition of the coloring composition of this invention in which the red pigment was disperse | distributed, for example in the formed partition by inkjet apparatus, prebaking is performed and the solvent is evaporated. Subsequently, after exposing this coating film as needed, it hardens | cures by post-baking to form a red pixel pattern.

Next, using each green or blue coloring composition, a green pixel pattern and a blue pixel pattern are formed sequentially on the same board | substrate similarly to the above. Thereby, the color filter by which the pixel pattern of three primary colors of red, green, and blue is arrange | positioned on a board | 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 function not only to block light, but also to prevent the coloring composition of each color discharged into the compartment from mixing. Thus, the film has a thicker film than the black matrix used in the first method. Therefore, a partition is normally formed using a black radiation sensitive composition.

The method and conditions for the substrate and the light source of the radiation used for forming the color filter, the prebaking and the postbaking are the same as those of the first method described above. Thus, the film thickness of the pixel formed by the inkjet system is about the same as the thickness of a black matrix.

After forming a protective film on the pixel pattern obtained in this way as needed, a transparent conductive film is formed by sputtering. After a transparent conductive film is formed, a spacer may be further formed to form a color filter. Although a spacer is normally formed using a radiation sensitive composition, it can also be set as the spacer (black spacer) which has light shielding property. In this case, a coloring and radiation-sensitive composition in which a black coloring agent is dispersed is used, and the coloring composition of the present invention can be preferably used for forming such a black spacer.

Since the color filter of this invention obtained in this way is extremely high in brightness | luminance and color purity, it is very useful for a color liquid crystal display element, a color image tube element, a color sensor, an organic EL display element, an electronic paper, etc.

Display element

The display element of this invention is equipped with the color filter of this invention. As a display element, a color liquid crystal display element, an organic electroluminescent display element, an electronic paper, etc. are mentioned.

The color liquid crystal display element provided with the color filter of this invention can take a suitable 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, and the driving substrate and the substrate on which the color filter is formed may have an opposite structure via the liquid crystal layer. The substrate on which the color filter is formed on the surface of the driving substrate on which the thin film transistor (TFT) is disposed, and the substrate on which the ITO (indium oxide doped tin) electrode is formed, have a structure in which the liquid crystal layer is opposed to each other. It may be. The latter structure has the advantage that the aperture ratio can be significantly improved, and a bright and high precision liquid crystal display element is obtained.

The color liquid crystal display element provided with the color filter of this invention can be equipped with the backlight unit which uses a white LED as a light source other than a cold cathode fluorescent tube (CCFL). As a white LED, for example, a white LED which combines a red LED, a green LED, and a blue LED to obtain white light by mixing, and a white LED and a blue LED which combines a blue LED, a red LED and a green phosphor to obtain white light by mixing White LED that obtains white light by mixing by combining red light emitting phosphor and green light emitting phosphor, white LED which obtains white light by mixing of blue LED and YAG fluorescent material, and blue LED, orange light emitting phosphor and green light emitting phosphor in combination The white LED which obtains white light, the ultraviolet-ray LED, the red light emitting fluorescent substance, the green light emitting fluorescent substance, and the blue light emitting fluorescent substance are combined, and the white LED etc. which obtain white light by mixing are mentioned.

The color liquid crystal display device including the color filter of the present invention includes a twisted nematic (TN) type, a super twisted nematic (STN) type, an in-plane switching switching (IPS) type, a vertical alignment (VA) type, and an OCB (Optically Compensated Birefringence) type. Appropriate liquid crystal modes such as a mold can be applied.

In addition, the organic electroluminescent display element provided with the color filter of this invention can take a suitable structure, for example, can take the structure disclosed by Unexamined-Japanese-Patent No. 11-307242.

In addition, the electronic paper provided with the color filter of this invention can take a suitable structure, for example, can take the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169.

<Examples>

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, the present invention is not limited to the following examples.

<Measurement of Mw and Mw / Mn>

Mw and Mn of the (B) copolymer obtained by each synthesis example below were measured by the gel permeation chromatography (henceforth GPC) of the following specification. A measurement result is shown in Table 1 with the copolymerization ratio (mass%) of each monomer in the (B) copolymer.

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

Column: KD-G, KF-603, KF-602, KF-601 (made by Showa Denko Co., Ltd.) was used in combination.

Mobile phase: DMF

<Synthesis of (B) Copolymer>

Hereinafter, the abbreviation of the raw material used for "the synthesis | combination of (B) copolymer" is as follows.

THF: tetrahydrofuran

EEMA: Methacrylic acid 1-ethoxyethyl

MA: methacrylic acid

nBMA: normal butyl methacrylate

MMA: methyl methacrylate

AIBN: 2,2'-azobisisobutyronitrile

DAMA: Dimethylaminoethyl methacrylate

CHMA: cyclohexyl methacrylate

BzMA: benzyl methacrylate

PME-200: methoxy polyethyleneglycol monomethacrylate (Nichiyu Co., Ltd. make, brand name PME-200, n'4 in the said General formula (3))

PME-100: methoxy polyethyleneglycol monomethacrylate (Nichi Oil Co., Ltd. make, brand name PME-100, n = 2 in the said General formula (3))

Synthesis Example 1

To a 1000 mL flask equipped with a stirrer, 516.1 g of THF, 34.1 g of lithium chloride (4.1 mass% concentration THF solution) and 3.6 g of diphenylethylene were added and cooled to -60 ° C. After adding 9.2 g of n-butyllithium (15.4 mass% concentration hexane solution) and ripening for 10 minutes, the reaction liquid of 18.5 g of PME-200, 34.0 g of nBMA, and 6.1 g of EEMA was dripped, and reaction was continued for 15 minutes.

Next, 55.4 g of DAMA was added dropwise, the reaction was continued for 30 minutes after the dropwise addition, and 3.2 g of methanol was added to stop the reaction. After adjusting the obtained copolymer with the propylene glycol monomethyl ether acetate (henceforth PGMEA) solution of 25 mass% concentration, 114 g of water was added and it heated at 100 degreeC and made it react for 8 hours. EEMA hydrolyzed by this reaction, and the repeating unit derived from MA was produced. Water was distilled off and adjusted to 40 mass% PGMEA solution. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, nBMA, and MA was obtained. Let the obtained copolymer be "copolymer (B-1)".

Synthesis Example 2

To a 300 mL flask equipped with a stirrer, 30 g of toluene, 4.2 g of PME-200, 5.6 g of MMA, 121 mg of AIBN, and 312 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added and dissolved for 30 minutes. Substitution was performed. Thereafter, the mixture was stirred slowly to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to carry out living radical polymerization.

Subsequently, after dissolving 983 mg of AIBN and 18.2 g of DAMA in 20 g of toluene, a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C for 24 hours. Then, it adjusted to 40 mass% PGMEA solution by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200 and MMA was obtained. Let the obtained block copolymer be "copolymer (B-2)".

Synthesis Example 3

To a 2000 mL flask equipped with a stirrer, 987.6 g of THF and 51.4 g of lithium chloride (3.9 mass% concentration THF solution) were added and cooled to -60 ° C. 21.4 g of n-butyllithium (15.4 mass% concentration hexane solution) was added and stirred for 10 minutes, followed by stirring for 15 minutes by adding 4.9 g of diisopropylamine, followed by further stirring for 15 minutes by adding 4.7 g of methyl isobutyrate. It was. 87.9 g of MMA and 45.3 g of PME-200 were added dropwise, and the reaction was continued for 15 minutes.

Next, 133.6 g of DAMA was added dropwise, the reaction was continued for 30 minutes after dropping, and then 7.7 g of methanol was added to stop the reaction. The obtained copolymer was adjusted to 40 mass% PGMEA solution. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200 and MMA was obtained. Let the obtained copolymer be "copolymer (B-3)".

Synthesis Example 4

To a 300 mL flask equipped with a stirrer, 30 g of toluene, 7.6 g of nBMA, 9.2 g of PME-200, 174 mg of AIBN, and 449 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added and dissolved for 30 minutes. Substitution was performed. Thereafter, the mixture was stirred slowly to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to carry out living radical polymerization.

Subsequently, after dissolving 716 mg of AIBN and 11.2 g of DAMA in 20 g of toluene, a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Then, it adjusted to 40 mass% PGMEA solution by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200 and nBMA was obtained. Let the obtained block copolymer be "copolymer (B-4)".

Synthesis Example 5

Into a 300 mL flask equipped with a stirrer, 20 g of toluene, 187 mg of AIBN, and 12.3 g of DAMA were added and dissolved, followed by nitrogen substitution for 30 minutes. Thereafter, the mixture was stirred gently to raise the temperature of the reaction solution to 60 ° C, and this temperature was maintained for 24 hours to carry out living radical polymerization.

Subsequently, 2.2 g of MMA, 7.0 g of PME-200, 5.6 g of CHMA, 0.8 g of MA, 809 mg of AIBN and 461 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 g of toluene, followed by 30 minutes. The solution which carried out nitrogen substitution was added to the said reaction solution, and living radical polymerization was performed at 60 degreeC for 24 hours. Then, it adjusted to 40 mass% PGMEA solution by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, MMA, CHMA, and MA was obtained. Let the obtained block copolymer be "copolymer (B-5)".

Synthesis Example 6

503.0 g of THF and 59.5 g of lithium chloride (4.1 mass% concentration THF solution) were added to a 1000 mL flask equipped with a stirrer, and the mixture was cooled to -60 ° C. 11.9 g of n-butyllithium (15.4 mass% concentration hexane solution) was added thereto, followed by stirring for 10 minutes, followed by addition of 2.8 g of diisopropylamine and stirring for 15 minutes, followed by addition of 2.8 g of methyl isobutyrate, followed by further stirring for 15 minutes. It was. A mixture of 74.6 g MMA and 32.2 g PME-100 was added dropwise to continue the reaction for 15 minutes.

Next, 52.1 g of DAMA was added dropwise, the reaction was continued for 30 minutes after the dropwise addition, and 4.5 g of methanol was added to stop the reaction. The obtained copolymer was adjusted to 40 mass% PGMEA solution. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200 and MMA was obtained. Let the obtained copolymer be "copolymer (B-6)".

Comparative Synthesis Example 1

To a 300 mL flask equipped with a stirrer, 30 g of toluene, 5.6 g of PME-200, 13.1 g of BzMA, 196 mg of AIBN, and 506 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added and dissolved for 30 minutes. Substitution was performed. Thereafter, the mixture was stirred slowly to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to carry out living radical polymerization.

Subsequently, after dissolving 607 mg of AIBN and 9.2 g of DAMA in 20 g of toluene, a solution subjected to nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C for 24 hours. Then, it adjusted to 40 mass% PGMEA solution by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200 and BzMA was obtained. Let the obtained block copolymer be "copolymer (b-1)".

Comparative Synthesis Example 2

To a 1000 mL flask equipped with a stirrer, 498.6 g of THF and 42.5 g of lithium chloride (4.1 mass% concentration THF solution) were added and cooled to -60 ° C. After adding 8.7 g of n-butyllithium (15.4 mass% hexane solution) and stirring for 10 minutes, 1.8 g of diisopropylamine was added and stirred for 15 minutes, followed by 1.8 g of methyl isobutyrate, followed by further stirring for 15 minutes. It was. A mixture of 60.7 g of MMA, 33.6 g of PME-200, and 11.8 g of EEMA was added dropwise, and the reaction was continued for 15 minutes.

Next, 28.7 g of DAMA was added dropwise, the reaction was continued for 30 minutes after dropping, and then 2.4 g of water was added to stop the reaction. After adjusting the obtained copolymer with PGMEA solution of 25 mass% concentration, 135 g of water was added, and it heated at 100 degreeC, and made it react for 8 hours. This reaction hydrolyzed EEMA and produced repeating units derived from MA. Water was distilled off and adjusted to 40 mass% PGMEA solution. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, MMA, and MA was obtained. Let the obtained block copolymer be "copolymer (b-2)."

Comparative Synthesis Example 3

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

Subsequently, after dissolving 2.8 g of nBMA, 4.2 g of PME-200, 1259 mg of AIBN, and 170 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester in 30 g of toluene, the solution which was subjected to nitrogen substitution for 30 minutes was reacted. It added to the solution, and performed living radical polymerization at 60 degreeC for 24 hours. Then, it adjusted to 40 mass% PGMEA solution by concentration under reduced pressure. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200 and nBMA was obtained. Let the obtained block copolymer be "copolymer (b-3)".

&Lt; Measurement of acid value &

The acid value of the (B) copolymer obtained by each said synthesis example was measured with the following method. Table 1 shows the measurement results.

0.5 g of the copolymer solution was precisely weighed to a unit of 1 mg and aliquoted into a glass container. After dilution to 50 mL with propylene glycol monomethyl ether acetate, phenolphthalein was added, titrated with 0.1 N aqueous ethanol potassium hydroxide solution, and the point colored pink was made into the end point. Similarly, a blank test was performed. (B) The acid value (unit: mgKOH / g) was computed from the copolymer and the dropwise amount of 0.1N ethanol aqueous potassium hydroxide solution of a blank test.

<Measurement of Amine Value>

The amine number of the (B) copolymer obtained by each said synthesis example was measured with the following method. Table 1 shows the measurement results.

0.5 g of the copolymer solution was precisely weighed to a unit of 1 mg and aliquoted into a glass container. 20 mL of acetic anhydride / acetic acid = 9/1 (volume ratio) was added to dissolve and allowed to stand at room temperature for 3 hours. Thereafter, 30 mL of acetic acid was further added, followed by titration with a 0.1 mol / L perchloric acid and acetic acid solution using a potentiometer AT-510 (manufactured by Kyoto Denshi Kogyo Co., Ltd.). Similarly, a blank test was performed. The amine number (unit: mgKOH / g) was computed from the (B) copolymer and the dropping amount of the 0.1 mol / L perchloric acid and acetic acid solution of a blank test.

Preparation of Pigment Dispersion

Production Example 1

12 parts by mass of CI Pigment Green 58 (manufactured by DIC Corporation) and 3 parts by mass of CI Pigment Yellow 138 as a coloring agent, 10 parts by mass of a copolymer (B-1) solution (nonvolatile component = 40% by mass), and a solvent The pigment dispersion (A-1) was produced by processing by the bead mill using 67 mass parts of propylene glycol monomethyl ether acetates, and 8 mass parts of propylene glycol monomethyl ethers.

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

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

<Evaluation of Pigment Dispersion>

The viscosity of the obtained pigment dispersion liquid was measured using an E-type viscometer (Tokyo Geiki). Moreover, the obtained coloring agent dispersion liquid was filled in the light shielding glass container, and after leaving still for 14 days at 23 degreeC in a sealed state, the viscosity was measured again using the E-type viscosity meter (Tokyo Geiki). And the increase rate of the viscosity after preservation for 14 days with respect to the viscosity immediately after manufacture is calculated, "A" for the case where the increase rate is less than 5%, "B" for the case of 5% or more and less than 10% is "C". Evaluated as. The evaluation results are shown in Table 2.

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

<Synthesis of Binder Resin>

Synthesis Example 7

A flask equipped with a cooling tube and a stirrer was dissolved by adding 30.0 g of BzMA, 20.0 g of nBMA, 15.0 g of hydroxyethyl methacrylate, 20.0 g of styrene, 15.0 g of MA, and 200 g of PGMEA, and further, AIBN 3.0 g and α-methyl. 5.0 g of styrene dimers were added and then nitrogen-substituted for 15 minutes. Then, the solution containing 33 mass% of binder resins (D-1) was obtained by heating at 80 degreeC, stirring reaction liquid, and superposing | polymerizing for 5 hours. As for this binder resin (D-1), the weight average molecular weight of polystyrene conversion measured by GPC (mobile phase: tetrahydrofuran) was 10,000, and ratio of weight average molecular weight and number 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-ethyl oxetane, MA 18.0 g, 9.0 g of succinic acid mono2-acryloxyethyl, 10.0 g of N-phenylmaleimide, BzMA 24.0 g, 14.0 g of hydroxyethyl methacrylate and 300 g of PGMEA were added and dissolved, and 6.0 g of AIBN and 6.0 g of α-methylstyrene dimer were added thereto, followed by nitrogen substitution for 15 minutes. Then, the precursor solution was obtained by heating to 80 degreeC, stirring reaction liquid, and superposing | polymerizing for 5 hours.

1 g of 2-methacryloyloxyethyl isocyanate and 0.2 g of 4-methoxy phenol were added as a polymerization inhibitor to 200 g of the obtained precursor copolymer solutions, and it was made to react at 90 degreeC for 2 hours. The reaction solution was washed twice with 75 g of ion-exchanged water per time, and then concentrated under reduced pressure to obtain a solution containing 33 mass% of binder resin (D-2). The weight average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran) of this binder resin (D-2) was 11,000, and ratio of the weight average molecular weight and number average molecular weight was 1.9.

&Lt; Preparation and evaluation of colored composition >

Preparation of Coloring Composition

Example 1

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

Evaluation of Chromaticity Characteristics

After apply | coating the obtained coloring composition on a glass substrate using a spin coater, it prebaked for 2 minutes on the 90 degreeC hotplate, and formed three coating films from which a film thickness differs. Subsequently, after cooling these board | substrates to room temperature, the radiation which contains each wavelength of 365 nm, 405 nm, and 436 nm in each coating film using the high pressure mercury lamp for the coating film on a board | substrate was exposed to the exposure amount of 1,000 J / m <^2> without passing through a photomask. It exposed. Thereafter, postbaking was performed at 230 ° C. for 60 minutes to form a cured film on the substrate. For the three cured films thus obtained, chromaticity coordinate values (x, y) and stimulus values (Y) in a CIE color system at a C light source and a 2-degree field of view were measured using a color analyzer (MCPD2000 manufactured by Otsuka Denshi Co., Ltd.). Measured. From the measurement result, the chromaticity coordinate value x and the stimulus value Y at the chromaticity coordinate value y = 0.569 were obtained. The evaluation results are shown in Table 3. Further, the stimulus value Y indicates that the higher the value, the higher the luminance.

Contrast Evaluation

Contrast was measured about the three cured films obtained by said "evaluation of chromaticity characteristic" using a contrast meter (Tsuba Co., Ltd. contrast meter CT-1). From the measurement result, the contrast when chromaticity coordinate value y = 0.569 was calculated | required. Table 3 shows the results of the evaluation. In addition, the larger the value, the higher the contrast.

Examples 2-6 and Comparative Examples 1-3

In Example 1, the coloring composition was produced and evaluated in the same manner as in Example 1 except that the kind and compounding amount of the pigment dispersion liquid, the binder resin, the crosslinking agent, the photopolymerization initiator, and the solvent were changed as shown in Table 3. Table 3 shows the results of the evaluation.

In Table 3, each component is as follows.

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

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

E-1: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name Irgacure OXE02, Ciba Specialty Chemicals Co., Ltd.)

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

EEP: 3-Ethoxypropionate Ethyl

MBA: 3-methoxybutyl acetate

Claims (8)

The following components (A), (B) and (C);
(A) a colorant containing a quinophthalone pigment,
(B) a copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), having an amine number of 80 to 250 mgKOH / g, and
(C) crosslinking agent
It contains, The coloring composition for color filters characterized by the above-mentioned.

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

In Formula (2),
R ⁴ represents a hydrogen atom or a methyl group,
R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.] The coloring composition for color filters of Claim 1 in which the said (B) copolymer further has at least any one of the repeating unit represented by following General formula (3), or an acidic group.

In formula (3),
R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ independently of each other represents an alkanediyl group having 2 to 4 carbon atoms,
R ⁸ represents an alkyl group having 1 to 6 carbon atoms,
n represents an integer of 1 to 150; The coloring composition for color filters of Claim 1 or 2 whose said quinophthalone pigment is C.I. pigment yellow 138. The coloring composition for color filters in any one of Claims 1-3 which further contains (D) binder resin (except the said (B) component). The coloring composition for color filters in any one of Claims 1-4 which further contain (E) photoinitiator. The color filter provided with the colored layer formed using the coloring composition of any one of Claims 1-5. The display element provided with the color filter of Claim 6. The following components (a1), (B) and (F);
(a1) quinophthalone pigments,
(B) a copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), having an amine number of 80 to 250 mgKOH / g, and
(F) solvent
Pigment dispersion liquid for color filters containing them.

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

In Formula (2),
R ⁴ represents a hydrogen atom or a methyl group,
R ⁵ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.]