KR20130110038A - Colored composition, color filter, display device and pigment dispersion - Google Patents

Abstract

PURPOSE: A colorant composition can form a coloring layer combining high heat resistance and solvent resistance, thereby being suitable for manufacturing various color filters. CONSTITUTION: A colorant composition contains a coloring agent including a lake pigment, a dispersing agent, and a crosslinking agent. The dispersant contains a copolymer with a repeating unit which has an oxygen-containing saturated heterocyclic group or contains both of a dispersant with a urethane group and a (meth)acrylic dispersant (except for the copolymer). A pigment-dispersed solution contains a lake pigment, a copolymer including a repeating unit having an oxygen-containing saturated heterocyclic group, and a solvent.

Description

Coloring composition, color filter, display element and pigment dispersion {COLORED COMPOSITION, COLOR FILTER, DISPLAY DEVICE AND PIGMENT DISPERSION}

This invention relates to a coloring composition, a color filter, and a display element, More specifically, it uses suitably for color filters, such as a transmissive or reflective color liquid crystal display element, a solid-state image sensor, an organic EL display element, and an electronic paper. It relates to the colored composition which becomes, the color filter provided with the colored layer formed using this coloring composition, and the display element provided with the said 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, it irradiates a radiation to a desired pattern shape of a dry coating film (hereinafter, "exposure" And developing to obtain various pixels (see Patent Documents 1 and 2, for example). A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Moreover, the method (for example, refer patent document 4) of obtaining each pixel by the inkjet system using the pigment dispersion type colored resin composition is also known.

In manufacture of a color filter, generally, high heat resistance is calculated | required by the point which goes through the high temperature process exceeding 200 degreeC. Moreover, in recent years, the color filter which has the outstanding chromaticity characteristic is calculated | required. In order to achieve these requirements simultaneously, the examination which applies a lake pigment to the coloring agent of the coloring composition for color filters is performed. For example, in patent document 5, it is reported about the color filter containing the colored layer formed of the coloring composition containing a lake pigment and a specific dispersing agent. Moreover, in patent document 6, it is reported about the color filter formed using the lake pigment and the coloring composition containing resin which has an ethylenically unsaturated double bond in a side chain.

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

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

(Patent Document 3) Japanese Patent Application Laid-open No. Hei 6-35188

(Patent Document 4) Japanese Unexamined Patent Publication No. 2000-310706

(Patent Document 5) Japanese Unexamined Patent Publication No. 2011-6602

(Patent Document 6) Japanese Unexamined Patent Publication No. 2012-8421

However, according to studies by the present inventors, it was found that the color filter including the colored layer formed by using the coloring compositions disclosed in Patent Documents 5 and 6 had a poor balance of heat resistance and solvent resistance.

Therefore, the subject of this invention is providing the coloring composition suitable for formation of the colored layer which can make heat resistance and solvent resistance compatible. Moreover, the subject of this invention is providing the color filter which comprises the colored layer formed using the said coloring composition, and the display element provided with the said color filter.

In view of such a situation, the present inventors conducted earnest examination and found that the said subject can be solved by using the coloring agent containing a lake pigment with a specific dispersing agent.

That is, this invention is a coloring composition containing (A) the coloring agent containing a lake pigment, (B) dispersing agent, and (C) crosslinking agent, (B) repeating which has (B-1) oxygen containing saturated heterocyclic group as a dispersing agent A copolymer containing a unit, or (B-2) a dispersant having a urethane bond and (B-3) a (meth) acrylic dispersant (except for the component (B-1)). It is providing the coloring composition characterized by the above-mentioned.

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

Moreover, this invention provides the pigment dispersion liquid containing the (a1) lake pigment, the copolymer containing the repeating unit which has a (B-1) oxygen-containing saturated heterocyclic group, and (F) solvent.

By using the coloring composition of this invention, the coloring layer which makes high heat resistance and high solvent resistance compatible can be formed. Therefore, the coloring composition of this invention is suitable for manufacture of various color filters, including the color filter for 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. Can be used.

(Mode for carrying out the invention)

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the structural component of the coloring composition of this invention is demonstrated in detail.

- (A) Colorant -

The coloring composition of this invention contains the (a1) lake pigment as (A) coloring agent. A lake pigment means what made soluble dye into the insoluble pigment by the precipitating agent, For example, barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, catanol, and tamol , Isopoly acid, heteropoly acid, and the like. Examples of isopolyacids include isopolytungstic acid, isopolyvanadine acid, isopolymolybdic acid, and the like, and heteropolyacids include, for example, phosphotungstic acid, phosphomolybdic acid and phospho. Tungsten molybdate, silico tungsten molybdate, silico tungstic acid, silico molybdate and the like. Among these, as a precipitating agent, isopoly acid and heteropoly acid are preferable, heteropoly acid containing a molybdenum atom is more preferable, and phosphotungsten molybdate is more preferable.

Examples of such lake pigments include those having the following color index (C.I.) names.

C.I. Pigment Yellow 61, C.I. Pigment Yellow 61: 1, C.I. Pigment Yellow 62, C.I. Pigment Yellow 100, C.I. Pigment Yellow 104, C.I. Pigment Yellow 133, C.I. Pigment Yellow 169, C.I. Pigment Yellow 183, C.I. Pigment Yellow 191, C.I. Pigment Yellow 191: 1, C.I. Pigment Yellow 206, C.I. Pigment Yellow 209, C.I. Pigment Yellow 209: 1, C.I. Pigment yellow 212;

C.I. Pigment Red 48: 1, C.I. Pigment Red 48: 2, C.I. Pigment Red 48: 3, C.I. Pigment Red 48: 4, C.I. Pigment Red 48: 5, C.I. Pigment Red 49, C.I. Pigment Red 49: 1, C.I. Pigment Red 49: 2, C.I. Pigment Red 49: 3, C.I. Pigment Red 52: 1, C.I. Pigment Red 52: 2, C.I. Pigment Red 53: 1, C.I. Pigment Red 54, C.I. Pigment Red 57: 1, C.I. Pigment Red 58, C.I. Pigment Red 58: 1, C.I. Pigment Red 58: 2, C.I. Pigment Red 58: 3, C.I. Pigment Red 58: 4, C.I. Pigment Red 60: 1, C.I. Pigment Red 63, C.I. Pigment Red 63: 1, C.I. Pigment Red 63: 2, C.I. Pigment Red 63: 3, C.I. Pigment Red 64: 1, C.I. Pigment Red 68, C.I. Pigment Red 81, C.I. Pigment Red 81: 1, C.I. Pigment Red 200, C.I. Pigment Red 237, C.I. Pigment Red 239, C.I. Pigment red 247;

C.I. Pigment Violet 2, C.I. Pigment Violet 3, C.I. Pigment Violet 3: 1, C.I. Pigment Violet 3: 3, C.I. Pigment Violet 27, C.I. Pigment violet 39;

C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 3, C.I. Pigment Blue 9, C.I. Pigment Blue 10, C.I. Pigment Blue 14, C.I. Pigment Blue 17: 1, C.I. Pigment Blue 24, C.I. Pigment Blue 24: 1, C.I. Pigment Blue 56, C.I. Pigment Blue 61, C.I. Pigment blue 62;

C.I. Pigment Green 1, C.I. Pigment Green 4.

Among these lake pigments, at least one selected from triarylmethane-based lake pigments and xanthene-based lake pigments is preferable, and in particular, C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 3, C.I. Pigment Blue 9, C.I. Pigment Blue 10, C.I. Pigment Blue 14, C.I. Pigment Blue 61, C.I. Pigment Blue 62, C.I. Pigment Violet 1, C.I. Pigment Violet 2, C.I. Pigment Violet 3, C.I. Pigment Violet 27, C.I. Triarylmethane type lake pigments such as pigment violet 39, C.I. Pigment Red 81, C.I. Pigment Red 81: 1, C.I. Pigment Red 81: 2, C.I. Pigment Red 81: 3, C.I. Pigment Red 81: 4, C.I. Pigment Red 81: 5, C.I. Pigment Red 169, C.I. Pigment Violet 1, C.I. Pigment Violet 1: 1, C.I. Pigment Violet 1: 2, C.I. Xanthene-based lake pigments such as pigment violet 2 are preferred from the viewpoint of chromaticity characteristics. Moreover, it is also possible to use the triaryl methane type | system | group lake pigment prepared by using isopoly acid or heteropoly acid as a precipitant disclosed in Unexamined-Japanese-Patent No. 2011-150195, Unexamined-Japanese-Patent No. 2011-186043, etc. can also be used.

In this invention, a lake pigment can be used individually or in mixture of 2 or more types.

The coloring composition of this invention can contain another coloring agent with (A1) coloring agent further with (a1) lake pigment. It does not specifically limit as another coloring agent, A color and a material can be selected suitably according to a use.

As the other colorant, any of pigments, dyes and natural dyes other than lake pigments can be used, but in the sense of obtaining pixels with high luminance and color purity, organic pigments other than lake pigments and organic dyes are preferred.

Examples of the organic pigments other than the lake pigments include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colourists), that is, those having the following color index (CI) names. Can be.

C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Red pigments such as pigment red 264;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as Pigment Green 58;

C.I. Pigment Blue 15: 6, C.I. Blue pigments such as Pigment Blue 80;

C.I. Pigment Yellow 83, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 179, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 211, C.I. Yellow pigments such as pigment yellow 215;

C.I. Orange pigments such as Pigment Orange 38;

C.I. Purple pigments such as pigment violet 23;

C.I. Pigment Black 1, C.I. Pigment Black 7 and other black pigments.

When using the triarylmethane type lake pigment as a coloring agent (A1), it is preferable to use the coloring composition of this invention for formation of a blue pixel or a red pixel. When using the coloring composition of this invention for formation of a blue pixel, it is a viewpoint of chromaticity characteristic to use together with at least 1 sort (s) selected from the group which consists of a purple pigment and a blue pigment with (a1) a lake pigment as (A) coloring agent. Preferred in, especially CI Pigment Blue 15: 6 and C.I. It is preferable to use together with at least 1 sort (s) chosen from the group which consists of pigment violet 23. In addition, when using the coloring composition of this invention for formation of a red pixel, it is chromaticity characteristic to use together with at least 1 sort (s) chosen from the group which consists of a red pigment and a purple pigment with (a1) a lake pigment as (A) coloring agent. It is preferable in terms of, and especially CI Pigment Red 177 and C.I. It is preferable to use together with at least 1 sort (s) chosen from the group which consists of pigment red 254.

In the present invention, when using a pigment as another colorant, the pigment may be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. In addition, you may use the pigment modifying the particle | grain surface with resin as needed. As resin which modifies the particle surface of a pigment, the vehicle resin of Unexamined-Japanese-Patent No. 2001-108817, or commercially available resin for disperse | distributing various pigments is 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, 9-124969, etc. can be employ | adopted, for example. . In addition, you may use an organic pigment refine | purifying primary particle by what is called salt milling. As a method of salt milling, the method disclosed by Unexamined-Japanese-Patent No. 8-179111 can be employ | adopted, for example.

In this invention, when using a pigment as other coloring agent, it can further contain a well-known dispersing aid. As a well-known dispersing aid, pigment derivatives, such as a copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of a quinophthalone, are mentioned, for example.

Moreover, as dye, it can select suitably from various oil-soluble dye, direct dye, acid dye, a metal complex dye, etc., For example, the thing of which the following color index (CI) names are attached | subjected are mentioned. have.

C.I. Solvent Yellow 4, C.I. Solvent Yellow 14, C.I. Solvent Yellow 15, C.I. Solvent Yellow 24, C.I. Solvent Yellow 82, C.I. Solvent Yellow 88, C.I. Solvent Yellow 94, C.I. Solvent Yellow 98, C.I. Solvent Yellow 162, C.I. Solvent yellow 179;

C.I. Solvent Red 45, C.I. Solvent red 49;

C.I. Solvent Orange 2, C.I. Solvent Orange 7, C.I. Solvent Orange 11, C.I. Solvent Orange 15, C.I. Solvent Orange 26, C.I. Solvent orange 56;

C.I. Solvent Blue 35, C.I. Solvent Blue 37, C.I. Solvent Blue 59, C.I. Solvent Blue 67.

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

(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% normally in solid content of a coloring composition, Preferably it is 5-60 mass %to be. Solid content here is components other than the solvent mentioned later.

In addition, although the content rate of (a1) lake pigment is adjusted suitably according to the chromaticity requested | required, when the coloring composition of this invention is used, the content rate of (a1) lake pigment is 30 mass% or more in all the coloring agents, Furthermore, even when it is 60 mass% or more, the colored layer excellent in heat resistance and solvent resistance can be formed.

-(B) dispersant-

In the present invention, (B) a copolymer containing a repeating unit having a (B-1) oxygen-containing saturated heterocyclic group (hereinafter also referred to as "(B-1) copolymer") as a dispersant, or ( B-2) It contains both the dispersing agent which has a urethane bond, and (B-3) (meth) acrylic-type dispersing agent (except the said (B-1) component).

First, the (B-1) copolymer will be described. (B-1) copolymer in this invention has a repeating unit (henceforth a "repeating unit (3)") which has an oxygen containing saturated heterocyclic group, and functions as a dispersing agent of (A) coloring agent.

The "oxygen-containing saturated heterocyclic group" in the present invention means a saturated heterocyclic group having an oxygen atom as a hetero atom constituting the heterocycle, but among these, a cyclic ether group having 3 to 7 atoms constituting the ring is preferable. Specific examples thereof include oxiranyl groups such as glycidyl group, 2-methylglycidyl group and glycidoxy group; Oxetanyl groups such as 3-methyloxetan-3-yl group, 3-ethyloxetan-3-yl group, 3-methyloxetan-3-ylmethoxy group, and 3-ethyloxetan-3-ylmethoxy group; 3,4-epoxycyclohexyl group; Tetrahydrofuranyl groups such as tetrahydrofuran-2-yl group and tetrahydrofuran-3-yl group; Tetrahydropyranyl groups, such as the tetrahydropyran-2-yl group and the tetrahydropyran-3-yl group, etc. are mentioned. Among these, an oxiranyl group, an oxetanyl group, a 3, 4- epoxycyclohexyl group, and a tetrahydrofuranyl group are preferable at the point which a desired effect is acquired more remarkably.

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

[In Formula (3),

R ⁸ represents a hydrogen atom or a methyl group,

Q represents an oxygen-containing saturated heterocyclic group,

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

In said Formula (3), as R <^8> , a methyl group is preferable among a hydrogen atom and a methyl group.

Examples of the divalent linking group (X ² ) include a -CONH-R ⁹ -(* ² ) group, a -COO-R ¹⁰ -(* ² ) group, and -COO-R ¹¹ -OOCNH-R ¹² -(＊ there may be mentioned (* ^2), and so on - ²⁾ _{group, -C 6 H 4 CH 2 -} (* 2) _{group, -C 6 H 4 CH 2 OR} 13. Here, R <^9> and R <^10> represents a C1-C10 alkanediyl group or C2-C10 alkanediyl oxy alkanediyl group which may independently have a single bond and a hydroxyl group, and R <^11> and R <^{12> show} Each independently represents an alkanediyl group having 1 to 10 carbon atoms, R ¹³ represents an alkanediyl group having 1 to 10 carbon atoms which may have a hydroxyl group, and (* ² ) represents a bond which is bonded to Q. Indicates.

As an alkanediyl group in R <^9> -R <^12> , a C1-C6 alkanediyl group is preferable, and as an alkanediyl group in R <^13> , a C2-C6 alkanediyl group is preferable. Specifically, 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. In this specification, an "alkanediyl oxyalkanediyl group" means the group which two alkanediyl groups couple | bonded through the oxygen atom. As an alkanediyl oxy alkanediyl group, a C2-C6 alkanediyl oxy alkanediyl group is preferable, For example, an ethylene oxy ethylene group, an ethylene oxy propylene group, a propylene oxy propylene group, an ethylene oxy butylene group, etc. are mentioned. have.

Among them, X ^{2 As, -COO-R 10 - (*} 2) ^{group, -COO-R 11 -OOCNH-R} 12 - group (* ²⁾ are preferred.

The copolymer (B-1) may have a repeating unit other than the above, and as an example of such a repeating unit, for example, a repeating unit represented by the following formula (1) (hereinafter also referred to as "repeating unit (1)"). ); Repeating units represented by the following formula (2) (hereinafter also referred to as "repeating unit (2)"); Repeating units represented by the following formula (4) (hereinafter also referred to as "repeating unit (4)"); Repeating unit having an acidic group (hereinafter also referred to as "repeating unit (5)"); 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; Allyl (meth) acrylate; 2- (2-vinyloxyethoxy) ethyl (meth) acrylate; Crotonic acid glycidyl ether; And repeating units derived from monomers such as N-methacryloyl morpholine.

Especially, it is preferable to have a repeating unit (1) from a viewpoint of heat resistance, and a repeating unit (2) from a viewpoint of dispersibility, respectively, and from a viewpoint of further dispersibility improvement, further a repeating unit (4) is carried out. It is desirable to have. Here, in this invention, "(meth) acrylate" shall mean "acrylate or methacrylate."

[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 linking group;

[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;

[In Formula (4),

R ¹⁴ represents a hydrogen atom or a methyl group,

R ¹⁵ independently of each other represent a C 2-4 alkanediyl group,

R ¹⁶ represents an alkyl group having 1 to 6 carbon atoms,

n represents an integer of 1 to 150;

[In Formula (5),

R ¹⁷ represents a hydrogen atom or a methyl group,

A represents an acidic group,

X ³ represents a single bond or a divalent linking group.

In said 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 each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. Here, in this invention, a "hydrocarbon group" is a concept containing an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and may be any form of linear, branched, and cyclic | annular form. The aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and the unsaturated bond may be present at any position.

As said aliphatic hydrocarbon group, a C1-C20 aliphatic hydrocarbon group is preferable, and a C1-C12 aliphatic hydrocarbon group is more preferable. More specifically, a C1-C20 alkyl group, a C2-C20 alkenyl group, and a C2-C20 alkynyl group are mentioned. As an alkyl group, a C1-C12 alkyl group is preferable, Specifically, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, isobutyl group, sec-butyl group, tert-butyl group, a pentyl group, and isopen A methyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, etc. are mentioned. Moreover, as an alkenyl group, a C2-C12 alkenyl group is preferable, Specifically, an ethenyl group, 1-propenyl group, 1-butenyl group, 1, 3- butadienyl group, 1-pentenyl group, and 2-pente And a nil group, a 1-hexenyl group, a 2-ethyl-2-butenyl group, a 2-octenyl group, a (4-ethenyl) -5-hexenyl group, a 2-decenyl group, and the like. As an alkynyl group, a C2-C12 alkynyl group is preferable, Specifically, an ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl 2-butynyl group, 2-octynyl group, (4-ethynyl) -5-hexynyl group, 2-decynyl group, etc. are mentioned.

Moreover, as said alicyclic hydrocarbon group, a C3-C20 alicyclic hydrocarbon group is preferable and a C3-C12 alicyclic hydrocarbon group is more preferable. Specifically, a C3-C20 cycloalkyl group is mentioned. As a cycloalkyl group, a C3-C12 cycloalkyl group is preferable, Specifically, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group Etc. can be mentioned. Here, in this invention, an "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 has the above-mentioned aliphatic hydrocarbon group as a coupling group with a substituent or a nitrogen atom, etc. It shall also include.

Moreover, as said aromatic hydrocarbon group, a C6-C20 aromatic hydrocarbon group is preferable, and a C6-C14 aromatic hydrocarbon group is more preferable. More specifically, a C6-C20 aryl group is mentioned, A C6-C14 aryl group is preferable as an aryl group. Here, in this invention, an "aryl group" refers to a monocyclic to tricyclic aromatic hydrocarbon group, and specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an azulenyl group, etc. are mentioned. .

As a substituent in a hydrocarbon group, a halogen atom, a hydroxyl group, a C1-C6 alkoxy group, etc. are mentioned. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an oxo atom are mentioned. As a specific example of a C1-C6 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an 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 the condensed heterocyclic group which these two condensed. These heterocyclic groups may be unsaturated or saturated, and may have a heteroatom other than a nitrogen atom in the ring. As hetero atoms other than a nitrogen atom, an oxygen atom and a sulfur atom are mentioned, for example.

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, ester group, an alkoxy group, a hydroxyl group, an amino group, an amide group, a thiol group, a thioether group etc. are mentioned, for example. Can be. 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 and hexyl group, and the like. Can be mentioned. As an ester group, a C1-C7 ester group is preferable, and a methoxycarbonyl group, an ethoxycarbonyl group, a formyloxy group, an acetoxy group, a benzoyloxy group etc. are mentioned specifically ,. As an alkoxy group, a C1-C6 alkoxy group is preferable and the thing similar to the above is mentioned as a specific example. 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 methyl thioether group, an ethyl thioether group, a butyl thioether group etc. are mentioned specifically ,.

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

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

Moreover, as said condensed heterocyclic group, group which has a basic skeleton represented by following formula (1-2)-(1-4) is mentioned specifically, These condensed heterocyclic group may have a substituent further. As a substituent, a halogen atom, a hydroxyl group, a C1-C6 alkoxy group, etc. are mentioned, The thing similar to the above is mentioned as the specific example.

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

In the formula (1), the divalent linking group (X ¹⁾ as, for example, in the alkanediyl group, an arylene group having a carbon number of 6~20, -CONH-R ⁶ having 1 to 10 carbon atoms (* ¹⁾ group, -COO-R ⁷ -(* ¹ ) group etc. are mentioned. Here, R ⁶ and R ⁷ each independently represent a single bond, an alkanediyl group having 1 to 10 carbon atoms, or an alkanediyloxyalkanediyl group having 2 to 10 carbon atoms, and (* ¹ ) is bonded to Z. It represents a binding hand.

As an arylene group in X <^1> , a C6-C14 arylene group is preferable, As an alkanediyl group in X <^1> , R <^6> and R <^7> , a C1-C6 alkanediyl group is preferable, and R is ^{As an} alkanediyl oxy alkanediyl group in ⁶ and R <^7> , a C2-C6 alkanediyl oxy alkanediyl group is preferable. As these specific examples, the same thing as the above-mentioned is mentioned. Moreover, as an arylene group, a phenylene group, a naphthylene group, a biphenylene group, an anthylene group, etc. are mentioned, for example.

Especially, as X <^1> , -COO-R <^7> -(* ¹ ) group is preferable and as R <^7> , a C2-C6 alkanediyl group is preferable.

In Formula (2), as R <^4> , a methyl group is preferable among a hydrogen atom or a methyl group.

Examples of the aliphatic hydrocarbon group for R ⁵ include the same as described above.

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 have a substituent and a halogen atom, a hydroxyl group, a C1-C6 alkoxy group etc. are mentioned as a substituent, for example. As a specific example of these substituents, the same thing as the above-mentioned is mentioned.

Especially, as R <^5> , a C1-C15 alkyl group and a C3-C20 alicyclic hydrocarbon group are preferable, and a C1-C12 alkyl group and a C4-C15 alicyclic hydrocarbon group are more preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, 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 ] decan-8-yl group, adamantyl group, dicyclopentenyl group, pentacyclopentadecanyl group, tricyclopentenyl group, isobornyl group is mentioned.

In Formula (4), as R <^14> , a methyl group is preferable among a hydrogen atom or a methyl group.

As the alkanediyl group for R ¹⁵ , for example, an ethylene group, an 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, etc. are mentioned.

As an alkyl group in R <^16> , the same thing as the above-mentioned is mentioned.

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 (5) is gatjiman an acidic group, such as the acidic group is not particularly restricted but includes, for example, phenolic hydroxyl group, a carboxyl group, a sulfo _{group, -SO 2 NH 2, -C (} CF 3) 2 -OH , etc. Can be mentioned. In this invention, as an acidic group, a phenolic hydroxyl group and a carboxyl group are preferable, and a carboxyl group is especially preferable at the point of dispersibility and alkali developability of the coloring composition obtained.

In said Formula (5), as R <^17> , a methyl group is preferable among a hydrogen atom and a methyl group.

2 As the divalent linking group (X ^3), for example, alkanediyl group, an aryl group, -CONH-R ¹⁸ having a carbon number of 1 to 10 - (* ³⁾ group, -COO-R ¹⁹ - (* ³⁾ group, - OCOR ²⁰ -(＊ ³ ) group, -R ²¹ -OCO-R ²² -(＊ ³ ) group, -COO- (C _m H _2m COO) _l -C _m H _2m -(＊ ³ ) group, -COO- And R ²³ -OCO-R ²⁴ -(* ³ ) groups. Herein, R ¹⁸ to R ²² each independently represent a single bond, an alkanediyl group having 1 to 10 carbon atoms, or an alkanediyloxyalkanediyl 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 ²³ represents an alkanediyl group having 1 to 10 carbon atoms, R ²⁴ represents a single bond, an alkanediyl group having 1 to 10 carbon atoms, a cyclohexane-1,2-diyl group, or A phenylene group is shown and (* ³ ) represents the bond which couple | bonds with A.

As an alkanediyl group in X <^3> , R <^18> -R <^22> , R <^23> and R <^24> , a C1-C6 alkanediyl group is preferable, As an arylene group in X <^3> , C6-C14 arylene A group is preferable and a C2-C6 alkanediyl oxy alkanediyl group is preferable as an alkanediyl oxy alkanediyl group in R <^18> -R <^22> . As a specific example of an alkanediyl group, an arylene group, and an alkyleneoxyalkylene group, the thing similar to the above is mentioned. Moreover, as a specific example of a phenylene group, a 1, 2- phenylene group and a 1, 4- phenylene group are mentioned, for example.

Among them, as X ³ , a single bond, a phenylene group, a -COO-R ¹⁹ -(* ³ ) group, -COO- (C _m H _2m COO) _l -C _m H _2m -(* ³ ) group, or -COO The -R ²³ -OCO-R ²⁴ -(* ³ ) group is preferable.

In the copolymer (B-1), the content of each repeating unit is not particularly limited, but from the viewpoint of solvent resistance and heat resistance, the content of repeating unit (3) is 1 to 50 in all repeating units. It is preferable that it is mass%, Furthermore, it is 3-40 mass%, Furthermore, it is 5-30 mass%.

When the (B-1) copolymer has a repeating unit (1) and a repeating unit (2) in addition to the repeating unit (3), the content ratio of the repeating unit (1) is all from the viewpoint of heat resistance. In a repeating unit, it is preferable that they are 5-60 mass%, Furthermore, 5-50 mass%, Furthermore, 10-40 mass%, Especially 10-30 mass%. Moreover, it is preferable that the content rate of a repeating unit (2) is 5-80 mass%, 10-75 mass%, Furthermore, 15-70 mass% in all the repeating units from a dispersible viewpoint.

In addition, when the (B-1) copolymer has a repeating unit (4) in addition to the repeating unit (1), the repeating unit (2), and the repeating unit (3), the content ratio of the repeating unit (4) is From a dispersible viewpoint, it is preferable that it is 5-50 mass%, Furthermore, it is 10-40 mass%, Furthermore, it is 10-30 mass% in all the repeating units.

In addition, when the (B-1) copolymer has a repeating unit (5) in addition to the repeating unit (1), the repeating unit (2), the repeating unit (3), and the repeating unit (4), the repeating unit (5) It is preferable that the content ratio of is 15 mass% or less, 10 mass% or less, and 6 mass% or less in all the repeating units from a dispersible viewpoint. In addition, the lower limit of the content rate of the repeating unit (5) is not specifically limited, Although 0 mass% may be sufficient in all the repeating units, It is preferable that it is 0.5 mass%.

The amine number of the copolymer (B-1) is not particularly limited, but from the viewpoint of heat resistance, the upper limit is preferably 250 mgKOH / g, more preferably 200 mgKOH / g, further 150 mgKOH / g, especially 100 mgKOH / g, especially 60 mgKOH / g. The lower limit is preferably 1 mg KOH / g, more preferably 10 mg KOH / g, and further 15 mg KOH / g. Here, in this invention, "amine value" is the mg number of the acid and equivalent KOH which are required in order to neutralize 1 g of non volatile matters except the solvent of a copolymer solution, Specifically, to the method as described in the Example to publish later To be measured.

On the other hand, when the (B-1) copolymer has a repeating unit (5), the acid value of the (B-1) copolymer is preferably 30 mg KOH / g or less, more preferably from the viewpoint of storage stability of the coloring composition. Is 25 mgKOH / g or less, more preferably 20 mgKOH / g or less. In addition, the lower limit of such an acid value is not specifically limited, Although 0 mgKOH / g may be sufficient, it is preferable that it is 1 mgKOH / g. Here, in this invention, an "acid value" is the mg number of KOH required in order to neutralize 1 g of non volatile matters except the solvent of a copolymer solution.

Although the (B-1) copolymer is not specifically limited as long as it has a repeating unit (3), From a point that a desired effect is more remarkable, a repeating unit (3), a repeating unit (2), and a repeating unit (4 ) A block having no repeating unit (5) and no repeating unit (1), repeating unit (3) without repeating unit (1), repeating unit (2), repeating unit ( It is preferable that it is an AB block copolymer and BAB block copolymer containing B block which has at least 1 sort (s) chosen from 4) and repeating unit (5).

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

In addition, repeating units other than the 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, each repeating unit may be contained in any aspect of random copolymerization and block copolymerization, and may be contained 2 or more types. When the (B-1) copolymer is a BAB block copolymer, the combination of the repeating units constituting the two B blocks is not particularly limited. For example, the repeating unit (3), the repeating unit (2) and the repeating unit ( B1-A having a block B1 with 4) and no repeating unit (5) and a block B2 with repeating unit (3) and repeating unit (5) and without repeating unit (2) and repeating unit (4) A -B2 block copolymer may be sufficient.

The copolymer (B-1) has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: dimethylformamide), preferably 1,000 to 100,000, More preferably, it is 3,000-50,000, More preferably, it is 5,000-30,000. By setting it as such an aspect, heat resistance and solvent resistance can be compatible at a high level.

Moreover, ratio (Mw / Mn) of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the (B-1) copolymer in this invention becomes like this. Preferably it is 1.0-5.0, More preferably, 1.0-3.0. In addition, Mn says here the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: dimethylformamide).

Although the copolymer (B-1) can be manufactured by a well-known method, when (B-1) copolymer is a block copolymer, it is manufactured by living-polymerizing the monomer which introduces each said repeating unit, for example. can do. As a living polymerization method, For example, Unexamined-Japanese-Patent No. 9-62002; Japanese Patent Application Laid-Open No. 2002-31713; P. Lutz, P. Massson et al., Polym. Bull. 12, 79 (1984); B. C. Anderson, G. D. Andrews et al., Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et al., Polym. J. 17, 977 (1985); K. Hatada, K. Ute, et al., Polym. J. 18, 1037 (1986); Ute Koichi, Hatada Koichi, Polymer Processing, 36,366 (1987); Higashimura Toshinobu, Mitsuo Sawamoto, Polymer Journal, 46,189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987); Ida Takumi, Inoue Shohei, Organic Synthetic Chemistry, 43, 300 (1985); D.Y.Sogoh, W.R.Hertler et al., Macromolecules, 20, 1473 (1987); J. Polym. Sci. Rt a Polym. Chem., 47, 3773-3794 (2009); The well-known method described in J. Polym. Sci. Rt a Polym. Chem., 47, 3544-3557 (2009), etc. can be employ | adopted.

As a monomer which gives a repeating unit (3), glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-glycidyloxybutyl (meth) acrylate, 3 , 4-epoxycyclohexylmethyl (meth) acrylate, p-vinylbenzyl glycidyl ether, 3- (vinyloxymethyl) -3-ethyloxetane, 3-[(meth) acryloyloxymethyl] oxetane , 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, tetrahydrofurfuryl (meth) acrylate, 3-tetrahydrofurfuryl (meth) acrylate, 2- (tetrahydrofurfuryloxy ) Ethyl (meth) acrylate etc. are mentioned. These may be used alone or in combination of two or more.

As a monomer which gives a repeating unit (1), for example, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acryl Rate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate, dimethylaminoethoxyethyl (meth) acrylate, dimethylaminoethoxypropyl (meth) acrylate, diethylaminobutoxybutyl (Meth) acrylate etc. are mentioned. These may be used alone or in combination of two or more.

As a monomer which gives a repeating unit (2), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylic Latex, 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, pentacyclopentadedecanyl (meth) acrylate, tricyclopentenyl (meth) acrylate, and the like. These can be used individually or in mixture of 2 or more types.

As a monomer which gives a repeating unit (4), 2-methoxyethyl (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glutol (meth) acrylate, meth, for example A methoxy propylene glycol (meth) acrylate, a methoxy dipropylene glycol (meth) acrylate, etc. are mentioned. As a monomer which gives a repeating unit (4), PME-100, PME-200 (above, Nichiyu Corporation make), etc. can also be used. These may be used alone or in combination of two or more.

Moreover, as a monomer which gives the repeating unit (5) which has an acidic group, for example, (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, (meth) acrylic acid carboxymethyl ester, (meth) Acrylic acid 2-carboxyethyl 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-acryloyloxyethyl Ammonium sulfonate, 2-acryloyloxyethylsulfonic acid imidazolium, 2-acryloyloxyethylsulfonic acid pyridinium, 2-methacryloxyethylsulfonic acid sodium, 2-methacryloxyethyl lithium sulfonate, 2-methacryloxyethyl Ammonium sulfonate, 2-methacryloxyethylsulfonic acid Imidazolium, 2-methacryloxyethylsulfonic acid pyridinium, styrene sulfonic acid, sodium styrene sulfonate, lithium styrene sulfonate, ammonium styrene sulfonate, styrene sulfonate imidazolium, pyridinium styrene sulfonate, etc. are mentioned. These may be used alone or in combination of two or more.

In this invention, 5-300 mass parts is preferable with respect to 100 mass parts of (A) coloring agents, and, as for content of (B-1) copolymer, 10-200 mass parts is especially preferable. By setting it as such an aspect, heat resistance and solvent resistance become easy to compatible.

In this invention, the dispersing agent (henceforth a "urethane type dispersing agent") which has a urethane bond (B-2) refers to the compound which has at least one urethane bond in a structure generically.

In this invention, it is preferable that the urethane bond which a urethane type dispersing agent has arises by making aromatic polyisocyanate and / or alicyclic polyisocyanate react with (poly) alcohol. Specifically, the dispersing agent described in Unexamined-Japanese-Patent No. 2-19844, Unexamined-Japanese-Patent No. 2007-269873, etc. are mentioned. When two or more urethane bonds exist in a urethane type dispersing agent, each urethane bond may be same or different.

Urethane-based dispersants are commercially available, for example

EFKA-4046 (non-volatile component = 39-41 mass%, amine value 17-21 mgKOH / g),

EFKA-4047 (non-volatile component = 34-36 mass%, amine number 14-20 mgKOH / g) [above, Efka Chemicals Corporation (EFKA) company],

Disperbyk-161 (non-volatile component = 30 mass%, amine value 11 mgKOH / g),

Disperbyk-162 (non-volatile component = 38 mass%, amine number 13 mgKOH / g),

Disperbyk-163 (non-volatile component = 45 mass%, amine value 10 mgKOH / g),

Disperbyk-164 (non-volatile component = 60 mass%, amine number 18 mgKOH / g),

Disperbyk-166 (non-volatile component = 30 mass%, amine value 20 mgKOH / g),

Disperbyk-167 (non-volatile component = 52 mass%, amine value 13 mgKOH / g),

Disperbyk-168 (non-volatile component = 30 mass%, amine value 11 mgKOH / g),

Disperbyk-182 (non-volatile component = 43 mass%, amine value 13 mgKOH / g),

Disperbyk-2164 (non-volatile component = 60 mass%, amine value 14 mgKOH / g) [above, BIC Chemie (BYK) make],

Solsperse 76500 (non-volatile component = 50 mass%, amine value 15 mgKOH / g) [made by Lubrizol Co., Ltd.], DISPARLON (made by Kusumoto Kasei Co., Ltd.), etc. are applied. It may be. Here, an "amine value" shows the mg number of the acid and equivalent KOH which are necessary for neutralizing 1 g of dispersant solid content.

Among the urethane-based dispersants, the amine number is preferably 80 mgKOH / g or less, more preferably 50 mgKOH / g or less, and further 30 mgKOH / g or less. Moreover, although the minimum of amine titer may be 0 mgKOH / g, 5 mgKOH / g, Furthermore, 10 mgKOH / g is preferable.

The urethane-based dispersant in the present invention, the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is usually 5,000 to 50,000, preferably 7,000 to 20,000.

In this invention, a urethane type dispersing agent can be used individually or in mixture of 2 or more types.

Content of a urethane type dispersing agent is 0.5-100 mass parts normally with respect to 100 mass parts of lake pigments in a coloring agent, Preferably it is 1-70 mass parts, More preferably, it is 10-50 mass parts, 35-50 mass parts especially desirable. In this case, when content of a urethane-type dispersing agent is less than 0.5 mass part, there exists a tendency for stability and heat resistance of a pigment dispersion liquid to fall, and when it exceeds 100 mass parts, there exists a possibility that the performance, such as developability as a coloring resist, may be impaired.

In the present invention, the term "(B-3) (meth) acrylic dispersant" (hereinafter also referred to as "(meth) acrylic dispersant") means a compound composed of a (co) polymer of a (meth) acrylic monomer (wherein (B) -1) except for components). In addition, "(meth) acrylic-type monomer" means the polymeric compound which has a (meth) acryloyl group in a molecule | numerator, and "(meth) acryloyl group" shall mean acryloyl group or methacryloyl group. .

In this invention, as a (meth) acrylic-type dispersing agent, the block copolymer which has the block which superposed | polymerized the (meth) acrylic-type monomer which has a pigment adsorption group, and the block which superposed | polymerized the (meth) acrylic-type monomer which does not have a pigment adsorption group is preferable. Examples of the pigment adsorber include a carboxymethyl group, a sulfo group, a phosphonooxy group, a (N substituted) amino group, a (N substituted) ammonia group, a group containing an aromatic ring, and the like, and a sulfo group, a phosphonooxy group, and (N Substituted) amino group and (Nsubstituted) ammonio group are preferable, and a (Nsubstituted) amino group and (Nsubstituted) ammonio group are more preferable. Specifically, the block copolymer described in Unexamined-Japanese-Patent No. 2002-31713, Unexamined-Japanese-Patent No. 2009-25813, Unexamined-Japanese-Patent No. 2010-134419, etc. are mentioned.

Such dispersants are commercially available, for example

Disperbyk-2000 (non-volatile component = 40 mass%, amine value 4 mgKOH / g),

Disperbyk-2001 (non-volatile component = 46 mass%, amine value 29 mgKOH / g),

BYK-LPN6919 (non-volatile component = 60 mass%, amine value 72 mgKOH / g),

BYK-LPN21116 (non-volatile component = 40 mass%, amine value 29 mgKOH / g),

BYK-LPN21324 (amine value 0 mgKOH / g) (above, Big Chemical Co., Ltd. make) is mentioned.

Among the above-mentioned (meth) acrylic dispersants, the amine number is preferably 130 mgKOH / g or less, more preferably 100 mgKOH / g or less, and 80 mgKOH / g or less. In addition, although the minimum of amine titer may be 0 mgKOH / g, 1 mgKOH / g, Furthermore, 3 mgKOH / g is preferable.

In this invention, a (meth) acrylic-type dispersant can be used individually or in mixture of 2 or more types.

Content of a (meth) acrylic-type dispersing agent is 0.5-100 mass parts normally with respect to 100 mass parts of lake pigments in a coloring agent, Preferably it is 1-70 mass parts, More preferably, it is 1-50 mass parts. In this case, when the content of the (meth) acrylic dispersant is less than 0.5 parts by mass, the stability and the solvent resistance of the pigment dispersion tend to be lowered. On the other hand, when the content of the (meth) acrylic dispersant is more than 100 parts by mass, performance such as developability as a colored resist may be impaired. There is concern.

The mass ratio [(B-2) / (B-3)] of the dispersant having the urethane bond (B-2) and the (B-3) (meth) acrylic dispersant is preferably 5/95 to 95/5. More preferably, they are 10/90-90/10, More preferably, they are 70/30-90/10. When the ratio of the dispersant having a urethane bond and the (meth) acrylic dispersant is smaller than 5/95, the heat resistance tends to be lowered. When the ratio of the dispersing agent which has a urethane bond and a (meth) acrylic-type dispersing agent exceeds 95/5, there exists a tendency for solvent resistance to fall easily.

In the present invention, in addition to the above (B-1) to (B-3), a known dispersant may be further contained. Examples of known dispersants include polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkylphenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, polyester dispersants, and the like. Can be mentioned.

Such dispersants are commercially available. For example, as a polyethyleneimine dispersant, Solpulse 24000 (manufactured by Lubrizol Co., Ltd.) or the like is used as a polyester-based dispersant, such as AJISPER-PB821, Ajisper-PB822, Ajisper-PB880, Ajisper-PB881 (above, Ajinomoto Fine Techno Co., Ltd.), etc. are mentioned, respectively.

-(C) crosslinking agent-

In the present invention, the (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 compound which has the said 2 or more (meth) acryloyl group, 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 with 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 said aliphatic polyhydroxy compound, For example, Bivalent aliphatic polyhydroxy compound, such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol; And trivalent or higher aliphatic polyhydroxy compounds such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. As (meth) acrylate which has the said hydroxyl group, 2-hydroxyethyl (meth) acrylate, trimethylolpropanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol, for example Penta (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 and biphenyltetracarboxylic acid 2 Tetrabasic acid dianhydrides such as anhydride and 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. As said alkylene oxide modified polyfunctional (meth) acrylate, at least 1 sort (s) chosen from bisphenol A di (meth) acrylate modified by at least 1 sort (s) chosen from ethylene oxide and a propylene oxide, ethylene oxide, and a propylene oxide. At least 1 selected from trimethylolpropane tri (meth) acrylate modified by at least one selected from isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide modified by At least one selected from pentaerythritol tri (meth) acrylate modified by the species, at least one selected from ethylene oxide and propylene oxide, pentaerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Stools by species A dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified by at least one or dipentaerythritol hexa (meth) acrylate is selected from and the like.

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 containing 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, polyfunctional (meth) acrylate obtained by making a trivalent or more aliphatic polyhydroxy compound and (meth) acrylic acid react, caprolactone modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate, Polyfunctional (meth) acrylate having a carboxyl group, N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N ', N'-tetra (alkoxymethyl) benzo Guanamine 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 di In the polyfunctional (meth) acrylate which pentaerythritol hexaacrylate has a carboxyl group, the compound obtained by making pentaerythritol triacrylate and succinic anhydride react, and dipentaerythritol pentaacrylate and succinic anhydride obtained The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and planar contamination and film residue hardly occur on the substrate and the light shielding layer of the unexposed part.

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

As for content of (C) crosslinking agent in this invention, 10-1,000 mass parts is preferable with respect to 100 mass parts of (A) coloring agents, and 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 sclerosis | hardenability may become inadequate. 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 planar contamination, a film | membrane residue, etc. are easy to generate | occur | produce 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 (D) binder resin in this invention, 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, the ethylenically unsaturated monomer which has one or more carboxyl groups (henceforth an "unsaturated monomer (d1)") And copolymers with other copolymerizable ethylenically unsaturated monomers (hereinafter also referred to as "unsaturated monomers (d2)").

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) acrylic acid. The rate, p-vinyl benzoic acid, etc. are mentioned.

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-position substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether and 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 2-10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2-10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2-10) mono (meth) acrylate , Polypropylene 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 ( Methoxide acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (Meth) acrylate, 3,4-epoxy Cyclohexylmethyl (meth) acrylate, 3 - [(meth) acryloyl-yloxymethyl] oxetane, 3- (meth) acrylic acid ester such as ethyl-3-oxetane [(meth) acryloyl-yloxymethyl];

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

The macromonomer which has a mono (meth) acryloyl group at the terminal of polymer molecular chains, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane, etc. are mentioned.

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 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, Japanese Patent Laid-Open No. 2004-101728, etc. The copolymer which has become is mentioned.

In addition, in this invention, Unexamined-Japanese-Patent No. 5-19467, Unexamined-Japanese-Patent No. 6-230212, Unexamined-Japanese-Patent No. 7-207211, Unexamined-Japanese-Patent No. 09-325494, for example Carboxyl group-containing polymers having a polymerizable unsaturated bond such as (meth) acryloyl group in the side chain, as disclosed in Japanese Patent Application Laid-Open No. 11-140144, Japanese Patent Application Laid-Open No. 2008-181095, and the like, (D ) Can also be used as binder resin.

As for the (D) binder resin in this invention, the weight average molecular weight (Mw) of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran) is 1,000-100,000 normally, 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 properties may be deteriorated, while if the Mw is too large, the resolution may be lowered or the pattern shape may be damaged. There exists a possibility that a dry foreign material may arise 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 (Mn) of (D) 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, Mn here says the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

Although the (D) binder resin in this invention can be manufactured by a well-known method, For example, Unexamined-Japanese-Patent No. 2003-222717, Unexamined-Japanese-Patent No. 2006-259680, International Publication 07/029871 The structure, Mw and Mw / Mn can also be controlled by the method disclosed in the call pamphlet.

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

In this invention, content of (D) 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 the content of the binder resin is too small, for example, alkali developability may decrease or the storage stability of the resulting colored composition may decrease. On the other hand, when the content of the binder resin is too high, the concentration of the colorant decreases relatively. There exists a possibility that it may become difficult to achieve the color density made into.

-(E) photoinitiator-

The coloring composition of this invention can be made to contain (E) photoinitiator. Thus, 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 (C) crosslinking agent by exposure of radiation, such as visible light, an ultraviolet-ray, an ultraviolet-ray, an electron beam, X-rays.

As such a photoinitiator, a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, O-acyl oxime type compound, an onium salt type compound, a benzoin type compound, a benzophenone type compound, (alpha), for example -Diketone compounds, polynuclear quinone compounds, diazo compounds, imidosulfonate compounds, and the like.

In this invention, (E) photoinitiator can be used individually or in mixture of 2 or more types. (E) 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, a thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxane Tones, 2,4-dichlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, and the like.

In addition, 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, etc. are mentioned.

Specific examples of the imidazole-based 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 and the like.

Moreover, when using a biimidazole type compound as (E) photoinitiator, it is preferable to use a hydrogen donor together at the point which can improve a sensitivity. The "hydrogen donor" here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure. Examples of the hydrogen donor include mercapane-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; Amine hydrogen donors, such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone, are mentioned. In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof. However, the combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors may further improve the sensitivity. It is preferable at the point which can be used.

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

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-tetra Hydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2 -Dimethyl-1,3-dioxoranyl) 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, ADEKA Corporation make), 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 propiope, for example Paddy, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylamino Benzoyl) coumarin, 4- (diethylamino) chalcone, and the like. Moreover, in this invention, the sensitivity of a coloring composition can be raised by containing the polyfunctional thiol which acts as a chain transfer agent. As such a chain transfer agent, for example, trimethylol propane tris (3-mercapto propionate), pentaerythritol tetrakis (3-mercapto propionate), 2,4,6-trimercapto-s- Triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine 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 (E) photoinitiator, 1-100 mass parts is especially preferable. In this case, when there is too little content of (E) 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-

When the coloring composition of this invention contains the said (A)-(D) component and the other component added arbitrarily, (F) solvent is mix | blended normally and it is prepared as a liquid composition.

Moreover, when the coloring composition of this invention contains the said (A) component-(C) component and the other component added arbitrarily, the coloring agent containing the (A1) lake pigment is normally contained in (F) solvent. And (B) a dispersant and a part of (D) binder resin together, for example using a bead mill, a roll mill, etc., mixing and disperse | distributing, grind | pulverizing, and to this pigment dispersion liquid, (C) A crosslinking agent, (D) binder resin, (E) photoinitiator, further (F) solvent, etc. are added as needed, and it is prepared by the method of mixing.

As said solvent, as long as it disperse | distributes or melt | dissolves the component which comprises a coloring composition, and does not react with these components, and has equatorial volatility, it can select suitably and can use.

As such a solvent, for example,

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene Glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, 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;

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 carboxylic acids, such as 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl ethoxy acetate, and 3-methyl-3- methoxybutyl propionate 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.

It is preferable to contain at least 1 sort (s) chosen from (poly) alkylene glycol monoalkyl ethers and (poly) alkylene glycol monoalkyl ether acetates from a viewpoint of solubility, pigment dispersibility, applicability, etc. among these solvents. And at least one selected from propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate.

In this invention, (F) solvent can be used individually or in mixture of 2 or more types.

Although content of (F) solvent is not specifically limited, The quantity which the total concentration of each component except the (F) solvent of a coloring composition becomes 5-50 mass% is preferable, and the quantity becomes 10-40 mass% This is more preferable. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability, and the coloring composition with favorable applicability can be obtained.

-additive-

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

As an additive, For example, Thermal polymerization initiators, such as an azo compound and an organic peroxide; Fillers such as glass and alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as fluorine-based surfactants and silicone-based surfactants; 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; Aggregation inhibitors 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 improving agents such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meth) acrylate; The siloxane oligomer etc. which have a reactive functional group disclosed by Unexamined-Japanese-Patent No. 2008-242078 etc. are mentioned.

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, on the surface of a board | substrate, a light shielding layer (black matrix) is formed as needed, partitioning the part which forms a pixel. Subsequently, after apply | coating the liquid composition of the radiation sensitive coloring composition of this invention in which the blue lake pigment was disperse | distributed on this board | substrate, prebaking is carried out and a solvent is evaporated and a coating film is formed. Subsequently, this coating film is exposed through a photomask, and then developed with an alkali developer to dissolve and remove the unexposed portion of the coating film. Thereafter, by postbaking, a pixel array in which blue pixel patterns are arranged in a predetermined arrangement is formed.

Subsequently, using the green or red radiation-sensitive coloring composition, the radiation-sensitive coloring composition was applied, prebaked, exposed, developed, and postbaked in the same manner as described above, so that the green pixel array and the red Pixel arrays are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in this invention, the order which forms each pixel is not limited to said thing. Moreover, in the 1st method of manufacturing a color filter, any one or more of the said blue, green, and red pixel array should just be a colored layer formed using the coloring composition of this invention.

In addition, the black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a port lithography method, but using a radiation-sensitive coloring composition in which a black colorant is dispersed. It may be formed in the same manner as in the case of forming the pixel. The coloring composition of this invention can be used suitably also for formation of such a black matrix.

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, vacuum deposition, or the like as desired.

When apply | coating a radiation sensitive coloring composition to a board | substrate, although the appropriate coating methods, such as a spray method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, can be employ | adopted, especially spin It is preferable to employ | adopt a coating method and the slit die coating method.

Prebaking is normally performed combining pressure reduction drying and heat drying. Drying under reduced pressure is performed until it reaches 50-200 kPa normally. In addition, the conditions of heat drying are about 1 to 10 minutes at 70-110 degreeC normally.

Application | coating thickness is a film thickness after drying, Usually, it is 0.6-8 micrometers, 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, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, Laser light sources, such as an argon ion laser, a YAG laser, an XeCl excimer laser, and a nitrogen laser, etc. are mentioned. As an exposure light source, an ultraviolet LED may be used. The wavelength is preferably in the range of 190 to 450 nm.

Generally, the exposure amount 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 hydrooxide, choline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1 Aqueous solutions, such as 5, diazabicyclo [4.3.0] -5-nonene, are preferable.

A suitable amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like can also be added to the alkaline developer. In addition, after alkali image development, water washing is carried out normally.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle developing method and the like can be applied. As for image development conditions, 5 to 300 second is preferable at normal temperature.

Although the conditions of post-baking are about 10 to 60 minutes normally at 120-280 degreeC, in terms of the heat resistance of this coloring agent, the temperature of post-baking becomes like this. Preferably it is 240 degrees C or less, Especially preferably, it is 230 degrees C or less, More preferably Preferably it is 200 degrees C or less.

The film thickness of the pixel formed in this way is 0.5-5 micrometers normally, Preferably it is 1-3 micrometers.

As a second method of manufacturing the color filter, a method of obtaining various pixels by the inkjet method disclosed in Japanese Patent Laid-Open No. Hei 7-318723, Japanese Patent Laid-Open No. 2000-310706 or the like can be adopted. have. In this method, first, a partition which also serves as a light shielding function is formed on the surface of the substrate. Subsequently, after discharging the liquid composition of the thermosetting coloring composition of this invention in which the blue rake pigment was disperse | distributed in the formed partition by inkjet apparatus, prebaking is performed and the solvent is evaporated. Subsequently, this coating film is exposed, if necessary, and then cured by post-baking to form a blue pixel pattern.

Next, using each thermosetting coloring composition of green or red, it is carried out similarly to the above, and a green pixel pattern and a red pixel pattern are sequentially formed on the same board | substrate. Thereby, a color filter in which the pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in this invention, the order which forms each pixel is not limited to said thing. Moreover, also in the 2nd method of manufacturing a color filter, any one or more of the said blue, green, and red pixel array should just be a colored layer formed using the coloring composition of this invention.

In addition, the partition wall has not only a light shielding function but also a function for preventing the mixed coloring composition discharged into the compartment from mixing. Thus, the barrier is thicker than the black matrix used in the first method described above. Therefore, a partition is normally formed using a black radiation sensitive composition.

The light source of the board | substrate and radiation used when forming a color filter, and the method and conditions of prebaking and postbaking are the same as that of the said 1st method. Thus, the film thickness of the pixel formed by the inkjet system is about the same as the height of a partition.

After forming a protective film on the thus-obtained pixel pattern as required, a transparent conductive film is formed by sputtering. After forming a transparent conductive film, a spacer can be formed further and it can be set as 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, although the radiation sensitive coloring composition in which the black coloring agent was disperse | distributed is used, the coloring composition of this invention can be used suitably also for formation of 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 electroluminescence display element, an electronic paper, etc. are mentioned.

The color liquid crystal display element provided with the color filter of this invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the substrate on which the driving substrate and the color filter are formed has a structure in which the liquid crystal layer faces each other. And a substrate having a color filter formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, an ITO (indium oxide doped tin) electrode or IZO (a mixture of indium oxide and zinc oxide) The board | substrate which provided the electrode can also take the structure which opposed through the liquid crystal layer. The latter structure has the advantage that the aperture ratio can be significantly improved, and a bright, high-definition 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 lamp (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, red LED, and green phosphor to obtain white light by mixing And white LED to obtain white light by mixing by combining red and green light emitting phosphors, white LED to obtain white light by mixing of blue LED and YAG-based phosphors, and mixing by combining green and white light emitting phosphors and green light emitting phosphors The white LED which obtains white light by this, an ultraviolet LED, the red LED, and the white LED which obtains white light by mixing by combining green emitting fluorescent substance and blue emitting fluorescent substance 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 alias type (VA) type, and an OCB (optically) type. Appropriate liquid crystal modes, such as Compensated Birefringence type, can be applied.

Moreover, the organic electroluminescent display element provided with the color filter of this invention can employ | adopt an appropriate structure, for example, the structure disclosed by Unexamined-Japanese-Patent No. 11-307242 is mentioned.

Moreover, the electronic paper provided with the color filter of this invention can employ | adopt an appropriate structure, For example, the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169 is mentioned.

(Example)

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, this invention is not limited to the following Example. In addition, abbreviated-name of the raw material used for a following example is as follows.

THF: tetrahydrofuran

nBMA: normal butyl methacrylate

MMA: methyl methacrylate

AMA: allyl methacrylate

OXMA: 3- (methacryloyloxymethyl) -3-ethyloxetane

THFMA: tetrahydrofurfuryl methacrylate

DAMA: Dimethylaminoethyl methacrylate

PME-200: methoxy polyethyleneglycol monomethacrylate (Nichiyu Co., Ltd. make, brand name PME-200, n * 4 in said Formula (4))

AIBN: 2,2'-azobisisobutyronitrile

PGMEA: Propylene glycol monomethyl ether acetate

<Synthesis of (B-1) Copolymer>

Synthesis Example 1

A 1000 mL three-necked flask with a stirrer and fully nitrogen-substituted was prepared, 231 g of toluene, 12 g of 1,2-dimethoxyethane and diisobutyl (2,6-di) at a concentration of 0.5 mol / L under a nitrogen atmosphere. 86 mL of toluene solution of -t-butyl-4-methylphenoxy) aluminum was added. After adjusting the temperature of the reaction container contents to 0 degreeC, 4.3 mL of 1.0 mol / L cyclohexane solutions of sec-butyllithium were added, and it stirred for 20 minutes. While maintaining at 0 degreeC under stirring, the mixed solution of 10.5 g of nBMA, 8.1 g of PME-200, and 4.5 g of OXMA was dripped over 60 minutes, and reaction was further continued for 1 hour. Subsequently, 6.9 g of DAMA was added dropwise over 30 minutes, and the reaction was further continued for 1 hour. After completion of the reaction by gas chromatography analysis (hereinafter abbreviated as GC), 0.5 mL of methanol was added to the reaction solution to terminate the polymerization reaction.

Toluene of the obtained solution was removed using a rotary evaporator to recover the copolymer. After dissolving the recovered copolymer in acetone, this solution was poured into hexane to obtain a precipitate. After repeating this operation 5 times and purifying, it dried at 60 degreeC under vacuum for 2 hours. Finally, the copolymer was dissolved in PGMEA and adjusted to a solution of 40% by mass concentration. Thus, the solution containing the A block which has a repeating unit derived from DAMA, and the B block which has a repeating unit derived from nBMA, PME-200, and OXMA was obtained. The obtained copolymer is called "copolymer (B1)."

Synthesis Example 2

A 500 mL three-necked flask equipped with a stirrer and fully nitrogen-substituted was prepared, and THF solution of 1,1-diphenyl-3-methyl pentyllithium with THF 231.0 g and a concentration of 0.25 mol / L under a nitrogen atmosphere was 13.3 mL. Added. The mixed solution of 13.5 g of nBMA, 8.1 g of PME-200, and 1.5 g of OXMA was dripped at this solution over 60 minutes, maintaining and maintaining at -70 degreeC, stirring, and reaction was continued for 1 hour. Subsequently, 6.9 g of DAMA was added dropwise over 30 minutes, and the reaction was further continued for 1 hour. After confirming completion of the reaction by GC, 0.5 mL of methanol was added to the reaction solution to terminate the polymerization reaction.

The obtained solution was poured into 1.5 L of hexane, and the produced copolymer was precipitated and recovered. Furthermore, after dissolving the recovered copolymer in methanol, the solution was poured into hexane. After repeating this operation 5 times and purifying, it dried at 60 degreeC under vacuum for 2 hours. Finally, the copolymer was dissolved in PGMEA and adjusted to a solution having a concentration of 40% by mass. Thus, the solution containing the A block which has a repeating unit derived from DAMA, and the B block which has a repeating unit derived from nBMA, PME-200, and OXMA was obtained. The obtained copolymer is called "copolymer (B2)."

Synthesis Example 3

To a 300 mL flask equipped with a stirrer, 30 g of toluene, 12.0 g of nBMA, 10.9 g of PME-200, 3.4 g of THFMA, 236 mg of AIBN and 608 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved and dissolved for 30 minutes. Nitrogen substitution was performed. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 60 ° C, the temperature was maintained for 24 hours, and living radical polymerization was performed.

Subsequently, after dissolving 410 mg of AIBN and 7.9 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 by the PGMEA solution of 40 mass% concentration by vacuum concentration. Thus, the solution containing the A block which has a repeating unit derived from DAMA, and the B block which has a repeating unit derived from nBMA, PME-200, and THFMA was obtained. The obtained diblock copolymer is called "copolymer (B3)."

Synthesis Example 4

To a 300 mL flask equipped with a stirrer, 30 g of toluene, 8.8 g of MMA, 7.9 g of PME-200, 2.9 g of OXMA, 217 mg of AIBN and 559 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved and dissolved for 30 minutes. Nitrogen substitution was performed. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 60 ° C, the temperature was maintained for 24 hours, and living radical polymerization was performed.

Subsequently, after dissolving 504 mg of AIBN and 9.7 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 by the PGMEA solution of 40 mass% concentration by vacuum concentration. Thus, the solution containing the A block which has a repeating unit derived from DAMA, and the B block which has a B block which has a repeating unit derived from MMA, PME-200, and OXMA was obtained. The obtained diblock copolymer is called "copolymer (B4)."

Synthesis Example 5

To a 300 mL flask equipped with a stirrer, add 30 g of toluene, 10.2 g of MMA, 6.9 g of nBMA, 3.3 g of PME-200, 1.3 g of THFMA, 278 mg of AIBN, and 716 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester Then, nitrogen replacement was performed for 30 minutes. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 60 ° C, the temperature was maintained for 24 hours, and living radical polymerization was performed.

Subsequently, after dissolving 199 mg of AIBN and 3.8 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 by the PGMEA solution of 40 mass% concentration by vacuum concentration. Thus, the solution containing the A block which has a repeating unit derived from DAMA, and the B block which has a B block which has a repeating unit derived from MMA, nBMA, PME-200, and THFMA was obtained. The obtained diblock copolymer is called "copolymer (B5)."

Synthesis Example 6

To a 300 mL flask equipped with a stirrer, 30 g of toluene, 8.0 g of nBMA, 3.2 g of PME-200, 6.4 g of OXMA, 168 mg of AIBN, and 433 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved and dissolved for 30 minutes. Nitrogen substitution was performed. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 60 ° C, the temperature was maintained for 24 hours, and living radical polymerization was performed.

Subsequently, after dissolving 749 mg of AIBN and 14.4 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 by the PGMEA solution of 40 mass% concentration by vacuum concentration. Thus, the solution containing the A block which has a repeating unit derived from DAMA, and the B block which has a repeating unit derived from nBMA, PME-200, and OXMA was obtained. The obtained diblock copolymer is called "copolymer (B6)."

Comparative Synthesis Example 1

In Synthesis Example 2, the mixed solution of nBMA 13.5 g, PME-200 8.1 g and OXMA 1.5 g was changed to nBMA 15.0 g and PME-200 8.1 g mixed solution in the same manner as in Synthesis Example 2 A 40 mass% PGMEA solution containing a diblock copolymer comprising a block having a repeating unit derived from DAMA and a B block having a repeating unit derived from nBMA and PME-200 was synthesized by synthesizing the block copolymer. Got it. The obtained diblock copolymer is called "copolymer (b1)."

Comparative Synthesis Example 2

In Synthesis Example 2, except that nBMA 13.5 g, PME-200 8.1 g, and OXMA 1.5 g mixed solution were changed to nBMA 10.5 g, PME-200 8.1 g, and AMA 4.5 g mixed solution, In the same manner, the diblock copolymer is synthesized and 40 mass containing a diblock copolymer composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from nBMA, PME-200 and AMA. A PGMEA solution at% concentration was obtained. The obtained diblock copolymer is called "copolymer (b2)."

Comparative Synthesis Example 3

To a 300 mL flask equipped with a stirrer, 30 g of toluene, 8.7 g of MMA, 7.8 g of PME-200, 188 mg of AIBN, and 485 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added and dissolved, followed by nitrogen substitution for 30 minutes. . Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 60 ° C, the temperature was maintained for 24 hours, and living radical polymerization was performed.

Subsequently, after dissolving 647 mg of AIBN and 12.4 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 by the PGMEA solution of 40 mass% concentration by vacuum concentration. Thus, the solution containing the diblock copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from MMA and PME-200 was obtained. The obtained diblock copolymer is called "copolymer (b3)."

Comparative Synthesis Example 4

To a 300 mL flask equipped with a stirrer, 30 g of toluene, 8.2 g of MMA, 11.5 g of nBMA, 6.3 g of PME-200, 303 mg of AIBN and 782 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved and dissolved. Nitrogen substitution was performed for minutes. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 60 ° C, the temperature was maintained for 24 hours, and living radical polymerization was performed.

Subsequently, after dissolving 71 mg of AIBN and 1.4 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 by the PGMEA solution of 40 mass% concentration by vacuum concentration. Thus, the solution containing the A block which has the repeating unit derived from DAMA, and the B block which has the repeating unit derived from MMA, nBMA, and PME-200 was obtained. The obtained diblock copolymer is called "copolymer (b4)".

<Measurement of Mw and Mw / Mn of (B-1) Copolymer>

Mw and Mn of the (B-1) copolymer obtained in each said synthesis example are shown in Table 1 with the copolymerization ratio (mass%) of each monomer. In addition, Mw and Mn were measured by GPC of the following specification.

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

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

Mobile phase: DMF

<Measurement of Amine Value of (B-1) Copolymer>

The amine number of the (B-1) 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 divided into glass containers. 20 mL of acetic anhydride / acetic acid = 9/1 (volume ratio) was added and dissolved, and the mixture was left 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, an empty test was performed. The amine number (unit: mgKOH / g) was computed from the copolymer and the amount of 0.1 mol / L perchloric acid and acetic acid solution dropwise of the blank test.

<Synthesis of (D) Binder Resin>

Synthesis Example 7

In a flask equipped with a cooling tube and a stirrer, 100 parts by mass of PGMEA was placed and replaced with nitrogen. Heated to 80 DEG C, at the same temperature, 100 parts by mass of PGMEA, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 2,2'-azobis (2,4-dimethylvalero Nitrile) 6 parts by mass of a mixed solution was added dropwise over 1 hour, and the polymerization was carried out for 2 hours while preserving this temperature. Then, the binder resin solution (solid content concentration 33 mass%) was obtained by heating up the temperature of reaction solution at 100 degreeC and superposing | polymerizing for 1 hour. As for the obtained binder resin, Mw of polystyrene conversion measured by GPC (mobile phase: THF) was 12,200, Mn was 6,500, and Mw / Mn was 1.87. This binder resin is called "binder resin (D1)."

Synthesis Example 8

To a flask equipped with a cooling tube and a stirrer, 30.0 g of benzyl methacrylate, 20.0 g of nBMA, 15.0 g of hydroxyethyl methacrylate, 20.0 g of styrene, 15.0 g of methacrylic acid, and 200 g of PGMEA were further dissolved and dissolved. 3.0 g and 5.0 g of alpha -methylstyrene dimers were added and nitrogen-substituted for 15 minutes after that. Then, the binder resin solution (solid content concentration 33 mass%) was obtained by heating at 80 degreeC, stirring, and superposing | polymerizing for 5 hours, stirring. This binder resin had a Mw of 10,000, Mn of 4,000, and Mw / Mn of 2.5 in terms of polystyrene measured by GPC (mobile phase: THF). This binder resin is called "binder resin (D2)."

<Preparation of pigment dispersion liquid containing (B-1) copolymer>

Preparation Example 1

12 mass parts of triaryl methane type lake pigments (in formula, x = 1 to 2) represented by following formula (6) as a coloring agent, 10 mass parts of non-volatile components (40 mass%) of a copolymer (B1) solution, a solvent As 73 mass parts of PGMEA and 5 mass parts of propylene glycol monomethyl ethers, it processed by the bead mill and prepared the pigment dispersion (A-1).

Preparation Examples 2 to 6 and Comparative Preparation Examples 1 to 4

In Preparation Example 1, except that the kind of the (B-1) copolymer was changed as shown in Table 2, the pigment dispersions (A-2) to (A-10) were prepared in the same manner as in Preparation Example 1. .

Pharmaceutics 7

As a colorant, C.I. Pigment Red 254 / C.I. Pigment Red 177 / C.I. Pigment Red 81: 2 (xanthene lake pigment rake with silicomolybdate) = 10/70/20 (mass ratio) 12 parts by mass of the mixture, 10 parts by mass of the solution of the copolymer (B1) (non-volatile component = 40 mass) %) And 73 mass parts of PGMEA and 5 mass parts of propylene glycol monomethyl ethers were used as a solvent, and it processed by the bead mill, and prepared the pigment dispersion (A-11).

Formulation Examples 8 and 9 and Comparative Formulation Examples 5 and 6

In Preparation Example 7, except that the kind of the (B-1) copolymer was changed as shown in Table 2, the pigment dispersions (A-12) to (A-15) were prepared in the same manner as in Preparation Example 7. .

<Preparation and Evaluation of a Coloring Composition Containing (B-1) Copolymer>

Example 1

Nippon Kayaku Co., Ltd. make MAX-3510 (Dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as 100 mass parts of pigment dispersion liquid (A-1), 52.9 mass parts of binder resin (D2) solutions, and a crosslinking agent Dipentaerythritol hexaacrylate is a main component) 32.9 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (brand name Irgacure) as a photopolymerization initiator (IRGACURE) 369, Chiba Specialty Chemicals Co., Ltd.) 5.8 mass parts and 205.2 mass parts of PGMEA were mixed as a solvent, and the liquid coloring composition (S-1) was prepared.

A coloring composition (S-1) thus obtained, carried out after coating with SiO ₂ for preventing the elution of sodium ions film using a spin coater on a soda glass substrate formed on the surface for 2 minutes on a hot plate at 90 ℃ prebaking And a coating film having a thickness of 2.5 µm was formed.

Subsequently, after cooling this board | substrate at room temperature, it exposes the radiation which contains each wavelength of 365 nm, 405 nm, and 436 nm in each coating film with the exposure amount of 400 J / m <2> through a photomask using a high pressure mercury lamp. did. Subsequently, 90 seconds of shower development was performed by discharging the developing solution which consists of a 0.04 mass% potassium hydroxide aqueous solution of 23 degreeC with a developing pressure of 1 kgf / cm <2> (nozzle diameter 1mm) with respect to this board | substrate. Then, after wash | cleaning this board | substrate with ultrapure water and air-drying, it post-baked further in the 200 degreeC clean oven for 30 minutes, and the dot pattern of 200 micrometer x 200 micrometers was formed on the board | substrate.

Evaluation of heat resistance

With respect to the obtained dot pattern, chromaticity coordinate values (x, y) and stimulus values (Y) in the CIE color system were measured using a color analyzer (MCPD2000, manufactured by Otsuka Denshi Co., Ltd.) at a C light source and a 2-degree field of view. Measured. Subsequently, chromaticity coordinate values (x, y) and stimulus values (Y) after additional baking at 200 ° C. for 90 minutes were measured, and color change before and after the additional baking, that is, ΔE ^* _ab was evaluated. The evaluation results are shown in Table 3. In addition, it shows that heat resistance is so high that the value of (DELTA) E ^* _ab is small.

Solvent-resistant  evaluation

The said board | substrate which formed the blue dot pattern was immersed in 25 degreeC N-methylpyrrolidone for 30 minutes, and the dot pattern before and behind immersion was observed with the scanning electron microscope. When a pattern having a good edge shape is formed, and the film thickness ratio (film thickness after immersion x 100 / film thickness before immersion) before and after immersion is 95% or more, "○" and the film thickness ratio before and after immersion are less than 95%. Or a case where a defect was confirmed in a part of the pattern was evaluated as "x" as "x" and the case where all the patterns were peeled off from a board | substrate after immersion. The evaluation results are shown in Table 3.

Examples 2-9 and Comparative Examples 1-6

In Example 1, except having changed the kind of pigment dispersion liquid as shown in Table 3, it carried out similarly to Example 1, and prepared and evaluated the coloring composition. The evaluation results are shown in Table 3.

<Preparation and evaluation of the coloring composition containing the dispersing agent which has a (B-2) urethane bond, and (B-3) (meth) acrylic-type dispersing agent>

Example 10

15 parts by mass of the triarylmethane-based lake pigment represented by the formula (6) as the coloring agent (in formula, x = 1 to 2), BYK2164 (non-volatile component = 60 mass%, amine value 14 mgKOH / g, Big Chemie) as a urethane dispersant BYK) Co., Ltd.) 8.9 parts by mass, (meth) acrylic dispersant BYK-LPN21116 (non-volatile components = 40 mass%, amine value 29 mgKOH / g, manufactured by Bigchem (BYK)) 1.8 parts by mass, propylene glycol monomethyl The ether acetate / propylene glycol monoethyl ether = 90/10 (mass ratio) mixed solvent was mixed so that solid content concentration might be 20 mass%, it mixed and dispersed for 12 hours by the bead mill, and prepared the pigment dispersion liquid (M-1). .

Next, 13.5 mass parts of pigment dispersion liquids (M-1), 9.9 mass parts of binder resin (D1) solutions as a binder resin, and M-402 (Dipentaerythritol hexaacrylate and dipentaerythritol penta) by Toagosei Co., Ltd. as a crosslinking agent. 1.8 mass parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Ciba Specialty Chemicals make, brand name IRGACURE369) as 15.4 mass parts of acrylates and a photoinitiator Parts, propylene glycol monomethyl ether acetate was mixed as 0.2 parts by mass of MEGAFAC F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant, and a solvent to prepare a coloring composition (CR1) having a solid content concentration of 20% by mass. .

In Example 1, it uses the coloring composition (CR1) instead of the coloring composition (S-1), and also carried out similarly to Example 1 except having set the prebaking time as 4 minutes, and has a film thickness of 2.5 micrometers. A coating film was formed.

Next, in the same manner as in Example 1, a dot pattern of 200 μm × 200 μm was formed on the substrate.

About the obtained dot pattern, heat resistance and solvent resistance were evaluated like Example 1. The evaluation results are shown in Table 5. However, in evaluation of heat resistance, "(circle)" and the case where ΔE _ab * is less than 3.0 are evaluated as "(circle)", the case of 3.0 or more and less than 5.0 as "Δ" and the case where 5.0 or more and less than 10 is set as "Δ" and 10 or more as "x". did.

Examples 11-20 and Comparative Examples 7-10

In Example 10, except that the kind and compounding quantity of a coloring agent, a urethane type dispersing agent, and a (meth) acrylic-type dispersing agent were changed as shown in Table 4, it carried out similarly to Example 10, and the pigment dispersion liquid (M-2) from the pigment dispersion liquid (M-2) M-15) was prepared.

Next, in Example 10, it is similar to Example 10 except having used pigment dispersion liquid (M-2)-(M-15) instead of pigment dispersion liquid (M-1), and colored composition (CR2)-( CR15) was prepared. And the obtained coloring composition was evaluated like Example 10. The evaluation results are shown in Table 5.

In Table 4, each component is as follows.

"PB61" means C.I. Pigment Blue 61 is C.I. with "PB15: 6". Pigment Blue 15: 6 refers to C.I. In Pigment Red 254, "PR81: 2" means C.I. Pigment red 81: 2 (xanthene lake pigment rake with silicomolybdic acid), respectively.

"BYK2164" means Disperbyk-2164 (non-volatile component = 60 mass%, amine value 14 mgKOH / g, Big Chemie (BYK) make), and "BYK164" means Disperbyk-164 (non-volatile component = 60 mass%, amine value 18 mgKOH / "S76500" means "S76500" (g volatility component = 50 mass%, amine value 15 mgKOH / g, Lubrizol Co., Ltd. product), respectively.

By "LPN21116" is BYK-LPN21116 (non-volatile component = 40 mass%, amine value 29 mgKOH / g, manufactured by Big Chemie (BYK)), and "BYK2000" is Disperbyk-2000 (non-volatile component = 40 mass%, amine value 4 mgKOH / "LPN6919" means BYK-LPN6919 (non-volatile component = 60 mass%, the amine value 72 mgKOH / g, the product made by BYK Corporation), respectively.

Claims (12)

A copolymer comprising (A) a coloring composition containing a rake pigment, (B) a dispersant and (C) a crosslinking agent, comprising (B) a repeating unit having a (B-1) oxygen-containing saturated heterocyclic group as a dispersant. Or (B-2) a coloring agent comprising both a dispersant having a urethane bond and (B-3) a (meth) acrylic dispersant (except for the component (B-1)). Composition. The method of claim 1,
The coloring composition in which the said (B-1) copolymer further has a repeating unit represented by following formula (1), and a repeating unit represented by following formula (2);

[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 linking group;

[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. 3. The method of claim 2,
The coloring composition whose upper limit of the amine titer of the said (B-1) copolymer is 150 mgKOH / g. The method of claim 1,
The coloring composition whose mass ratio [(B-2) / (B-3)] of the dispersing agent which has the said (B-2) urethane bond, and (B-3) (meth) acrylic-type dispersing agent is 5 / 95-95 / 5. The method of claim 1,
The coloring composition whose amine titer of the said (B-3) (meth) acrylic-type dispersing agent is 1-130 mgKOH / g. The method of claim 1,
The said lake pigment is a coloring composition prepared using heteropoly acid. The method of claim 1,
The said lake pigment is the coloring composition which is at least 1 sort (s) chosen from a triarylmethane type lake pigment and a xanthene type lake pigment. The method of claim 1,
The coloring composition containing (A) the coloring agent and which further contains a pigment (except a lake pigment). The method of claim 1,
Furthermore, the coloring composition containing (D) binder resin (except the said (B) component). The color filter provided with the colored layer formed using the coloring composition of any one of Claims 1-9. The display element provided with the color filter of Claim 10. A pigment dispersion liquid containing the (a1) lake pigment, the copolymer containing the repeating unit which has the (B-1) oxygen containing saturated heterocyclic group, and (F) solvent.