KR20120022573A - Colored composition, method of producing the colored composition, colored pattern, color filter, color display device, and method of manufacturing the color filter - Google Patents

Abstract

PURPOSE: A colored composition, a method for manufacturing the colored composition, a color pattern, a color filter, a color display device, and a color filter manufacturing method are provided to improve the developing resistance, the heat resistance, the solvent resistance, and the voltage holding ratio of the color pattern and the color filter. CONSTITUTION: A colored composition includes a compound with an epoxy group, a coloring agent, a hydroxyl group or carboxylic group containing compound, and an amine compound. The viscosity of the colored composition at 25 degrees Celsius is between 1.0 and 50 mPa·s. The amine compound is included in the hydroxyl group or carboxylic group containing compound. The hydroxyl group or carboxylic group containing compound is at least one compound selected from compounds represented by either chemical formula 1 or 2. The amine compound is imidazole compound or benzoimidazol compound. In chemical formula 1, the X is a single bond, methylene group, or C2 to C6 alkylene group; the R1 to R8 are respectively hydrogen element, C1 to C12 alkyl group, halogen element, C1 to C12 alkoxy group, or phenyl group with/without a substituted group. In chemical formula 2, the R9 is C1 to C12 alkyl group, C1 to C12 alkoxy group, nitro group, or hydroxyl group.

Description

Coloring composition, manufacturing method of coloring composition, coloring pattern, color filter, color display element and manufacturing method of color filter {COLORED COMPOSITION, METHOD OF PRODUCING THE COLORED COMPOSITION, COLORED PATTERN, COLOR FILTER, COLOR DISPLAY DEVICE, AND METHOD OF MANUFACTURING THE COLOR FILTER}

This invention relates to a coloring composition, the manufacturing method of a coloring composition, a coloring pattern, a color filter, a color display element, and the manufacturing method of a color filter.

As a manufacturing method of the color filter using a coloring composition, after apply | coating a pigment dispersion type coloring composition on a board | substrate and drying, it irradiates (exposures) and develops each color by irradiating a radiation through a desired mask pattern with respect to this coating film. The method of obtaining a pixel is known (refer patent document 1 and 2). Moreover, the method of obtaining the pixel of each color by the inkjet system using the pigment dispersion type colored resin composition is also known (refer patent document 3).

Moreover, in order to implement | achieve high contrast of a liquid crystal display element and high definition of a solid-state image sensor, it is said that using dye as a coloring agent is effective (refer patent document 4-6). In the coloring composition containing a dye, the hardening system which combined the polyfunctional acrylate, the alkoxy methyl melamine resin, etc. and a photoinitiator is mainly employ | adopted.

On the other hand, in recent years, flexible displays, such as electronic paper, have become popular. As a board | substrate of this flexible display, plastic board | substrates, such as a polyethylene terephthalate, are examined. Since this board | substrate expands or contracts at the time of baking, there exists a problem which inhibits the function as a display, and it is required to lower the baking process (refer patent document 7).

However, the color filter baked at low temperature using the conventional coloring composition containing dye has a problem that heat resistance and solvent resistance are inferior. Moreover, whether the color filter obtained is due to insufficient curing reactivity, the color filter obtained is not satisfactory in development resistance, voltage holding ratio, and the like. Therefore, although addition of an amine compound used as a curing agent for epoxy-based materials can be considered to promote crosslinking reaction even at a low temperature, general addition of the amine compound may cause reaction with time with an epoxy group present in the composition. It may cause, and storage stability may fall.

From such a situation, development of the coloring composition which is compatible with storage stability and low temperature baking, and the coloring pattern and color filter excellent in image development resistance, heat resistance, solvent resistance, voltage retention, etc. are desired.

Japanese Patent Application Laid-open No. Hei 2-144502 Japanese Patent Application Laid-Open No. 3-53201 Japanese Laid-Open Patent Publication No. 2000-310706 Japanese Laid-Open Patent Publication No. 2005-99584 Japanese Laid-Open Patent Publication No. 2007-219466 Japanese Laid-Open Patent Publication No. 2007-316179 Japanese Laid-Open Patent Publication No. 2009-4394

This invention is made | formed based on the above circumstances, The objective is the coloring composition which is compatible with storage stability and low temperature baking, the coloring pattern excellent in image development resistance, heat resistance, solvent resistance, voltage retention, etc., a color filter, and a color filter. It is to provide a color display element and a manufacturing method of a color filter provided.

The invention made to solve the above problems,

[A] a compound having an epoxy group (hereinafter also referred to as "[A] epoxy compound"),

[B] a colorant,

[C] a compound having a hydroxyl group or a carboxyl group (hereinafter also referred to as "[C] compound"), and

[D] contains an amine compound,

It is a coloring composition whose viscosity in 25 degreeC is 1.0 mPa * s or more and 50 mPa * s or less.

The coloring composition can contain both the [A] epoxy compound, the [C] compound, and the [D] amine compound while containing the [B] colorant as the colorant, thereby achieving improvement in storage stability and lowering of sintering. Usually, an amine compound is known as a hardening accelerator for accelerating the crosslinking reaction of an epoxy compound. Also in the said coloring composition, an [D] amine compound acts on the epoxy group in a compound [A], and promotes a crosslinking reaction. In this case, when the viscosity of the composition solution increases and becomes 50 mPa · s or more, it becomes difficult to control the film thickness at the time of application and cannot be applied as a coloring composition, but by containing the [C] compound and the [D] amine compound, The viscosity at 25 degrees C of the said coloring composition can be controlled to 1.0 mPa * s or more and 50 mPa * s or less, and can be compatible with storage stability and low temperature baking. Moreover, the said coloring composition can form the color filter excellent in image development resistance, heat resistance, solvent resistance, voltage retention, etc.

It is preferable that [D] an amine compound can be included in a [C] compound. By making an amine compound [D] into an amine compound which can be included in the [C] compound, at least one part of these compounds forms a clathrate compound, and the said coloring composition can contain a clathrate compound, and it is compatible with storage stability and low temperature baking. can do. That is, at room temperature, the [D] amine compound which accelerates hardening is enclosed, hardly hardens the epoxy group, and does not increase the viscosity of the composition solution. Therefore, the said coloring composition becomes the thing excellent in storage stability. On the other hand, when the said coloring composition is heated above predetermined temperature, clathrate collapses and an [D] amine compound will be released, an epoxy-group containing resin will bridge | crosslink, and hardening reaction is accelerated | stimulated.

The compound [C] is at least one compound selected from the group consisting of compounds represented by the following formulas (1) and (2), respectively, and the [D] amine compound is an imidazole compound or a benzimidazole compound. desirable :

(In formula (1), X is a single bond, a methylene group, or a C2-C6 alkylene group; R <^1> -R <^8> respectively independently represents a hydrogen atom, a C1-C12 alkyl group, a halogen atom, and C1-C1. A phenyl group which may have a? 12 alkoxy group or a substituent;

In formula (2), R <^9> is a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, or a hydroxyl group.).

A clathrate compound can be formed efficiently by making [C] compound and [D] amine compound into the said specific compound, respectively.

It is preferable that the compound represented by said Formula (1) is a compound represented by following formula (1-1):

(In formula (1-1), X and R <^1> -R <^8> have the same meaning as said Formula (1).).

By making the compound represented by the said Formula (1) into a tetrakisphenol type compound with higher symmetry represented by said Formula (1-1), it is considered that the clathrate improves more, and as a result, storage stability improves further and it is low temperature. Hardening in can also be accelerated.

In the said coloring composition, it is preferable that at least one part of the [D] amine compound is contained in the [C] compound. In the coloring composition, at least a part of the amine compound [D] is included in the [C] compound to form a clathrate compound, thereby achieving both storage stability and low temperature baking.

It is preferable that an epoxy compound (A) is a polymer, and it is more preferable that it is a polymer which has a carboxyl group further. When the (A) epoxy compound is a polymer, the hardness of the coloring pattern and the color filter is further improved. In addition, the clathrate compound is generally used as a solid powder, which is dispersed in a composition solution or the like, since the clathrate may collapse when dissolved in a polar solvent such as an alcohol solvent or an ether solvent. However, in the said coloring composition, when the [A] epoxy compound further has a carboxyl group, it is thought that the collapse of a clathrate is suppressed by interaction with this carboxyl group and a clathrate compound, It can be dissolved and used in a polar solvent, and it is uniform One coatability can be realized. Moreover, it is thought that the said interaction adds the proton of a carboxyl group to [D] amine compounds, such as imidazole, and the carboxyl group anionizes and a carboanion is produced | generated. Since this carbo anion also has a high nucleophile, it is thought that a clathrate compound also has the synergistic effect which accelerates hardening reaction of an epoxy group.

It is preferable that the said coloring composition further contains the polymeric compound (henceforth also called "[E] polymeric compound") which has [E] ethylenically unsaturated bond. When the said coloring composition contains a [E] polymeric compound further, the color filter excellent in heat resistance, solvent resistance, etc. is obtained even in the case of low exposure amount.

It is preferable that the said coloring composition further contains a [F] radiation sensitive polymerization initiator. When the said coloring composition contains a [F] radiation sensitive polymerization initiator further, the color filter excellent in heat resistance, solvent resistance, etc. is obtained even in the case of low exposure amount.

The said coloring composition whose viscosity in 25 degreeC is 1.0 mPa * s or more and 50 mPa * s or less mix | blends the clathrate compound which the [D] amine compound contained in the [C] compound with [A] epoxy compound, and [B] colorant, It is preferable to prepare. According to the said process, the said coloring composition containing a clathrate compound can be manufactured efficiently. In the present invention, a clathrate compound in which the [D] amine compound is contained in the [C] compound is mixed with the [A] epoxy compound and the [B] colorant, and the viscosity at 25 ° C. is 1.0 mPa · s or more and 50 mPa · s. The manufacturing method of the coloring composition which has the process of preparing below is also contained suitably.

The coloring pattern formed from the said coloring composition, a color filter, and the color display element provided with this color filter are also contained suitably for this invention.

The manufacturing method of the color filter of this invention,

(1) Process of apply | coating the said coloring composition and forming a coating film on a board | substrate,

(2) forming a colored pattern on the coating film, and

(3) Process of baking the said coloring pattern at 200 degrees C or less

Respectively.

By the manufacturing method of this invention using the said coloring composition, the color filter which satisfy | fills heat resistance, chemical-resistance, voltage preservation ratio, etc. well-balanced can be manufactured.

In addition, the said viscosity said in this specification means the value which measured the viscosity (mPa? S) of the said composition at 25 degreeC using the E-type viscosity meter (The Toki Sangyo Co., Ltd. make, VISCONIC ELD.R). "Firing" means heating until the hardness required for a coloring pattern and a color filter is obtained. The "inclusion compound" refers to a compound in which other guest molecules are trapped in molecular units in a space formed by a host molecule. "Radiation" irradiated at the time of exposure is a concept including visible light, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.

According to the coloring composition of this invention, while containing the dye as a coloring agent, it is compatible with storage stability and low temperature baking, and the coloring pattern and color filter which are excellent in image development resistance, heat resistance, solvent resistance, voltage retention, etc. are obtained. Therefore, the said coloring composition can be used suitably for manufacture of various color filters, such as a color filter for color 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. .

(Form to carry out invention)

<Coloring composition>

The coloring composition of this invention contains an [A] epoxy compound, a [B] coloring agent, a [C] compound, and a [D] amine compound, and the viscosity in 25 degreeC is 1.0 mPa * s or more and 50 mPa * s or less. Moreover, the said coloring composition may contain a [E] polymeric compound and a [F] radiation sensitive polymerization initiator as a suitable component. Moreover, the said coloring composition may contain other arbitrary components, unless the effect of this invention is impaired. Hereinafter, each component is explained in full detail.

<[A] Epoxy Compound>

[A] The epoxy compound is not particularly limited as long as it has an epoxy group in the molecule. As an epoxy group, an oxiranyl group (three-membered ring structure containing an oxygen atom) and an oxetanyl group (four-membered ring structure containing an oxygen atom) are mentioned.

[A] As an epoxy compound, For example, two or more glycidyl groups in a molecule | numerator; Polyfunctional epoxy compounds having two or more 3,4-epoxycyclohexyl groups in a molecule; Polyglycidyl ethers of polyhydric alcohols such as polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether; Aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; Phenol novolak-type epoxy resins, such as a bisphenol A novolak-type epoxy resin; Cresol novolac type epoxy resins; Polyphenol type epoxy resins; Cyclic aliphatic epoxy resins; Diglycidyl esters of aliphatic long chain dibasic acids; Glycidyl esters of higher fatty acids; Epoxidized soybean oil, epoxidized linseed oil, etc. are mentioned.

[A] As the epoxy compound, a polyfunctional epoxy compound having two or more glycidyl groups in a molecule and two or more 3,4-epoxycyclohexyl groups in a molecule, a phenol novolak type epoxy resin, and a polyphenol type epoxy resin are preferable. Do.

Examples of the compound having two or more glycidyl groups in the molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, Polyglycidyl ethers of bisphenols such as hydrogenated bisphenol F diglycidyl ether and hydrogenated bisphenol AD diglycidyl ether; 1, 4- butanediol diglycidyl ether, 1, 6- hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, etc. are mentioned.

Examples of the compound having two or more 3,4-epoxycyclohexyl groups in the molecule include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and 2- (3,4-epoxy Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meth-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexyl Methyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene Epoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4' -Epoxycyclohexane carboxylate, etc. are mentioned.

[A] As a commercial item of an epoxy compound, it is, for example

As a bisphenol-A epoxy resin, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (above, Japan Epoxy Resin Co., Ltd.);

As bisphenol F type epoxy resin, Epicoat 807 (Japan Epoxy Resin Co., Ltd.);

As a phenol novolak-type epoxy resin (bisphenol A novolak-type epoxy resin, etc.), Epicoat 152, copper 154, copper 157S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN 201, copper 202 (above, Nippon Kayaku Co., Ltd.) Shikiisha);

As a cresol novolak type epoxy resin, EOCN 102, copper 103S, copper 104S, copper 1020, copper 1025, copper 1027 (above, Nippon Kayaku Co., Ltd.),

Epicoat 180S75 (above, Japan Epoxy Resin Co., Ltd.);

As a polyphenol type epoxy resin, Epicoat 1032H60 and XY-4000 (above, Japan Epoxy Resin Co., Ltd.);

As cyclic aliphatic epoxy resin, CY-175, copper 177, copper 179, ARALDITE CY-182, copper 192, copper 184 (above, Chiba Chemicals Chemicals Co., Ltd.), ERL-4234, copper 4299, east 4221, east 4206 (above, UCC company), Shodyne 509 (Showa Denko Corporation), epiclon (EPICLON) 200, east 400 (above, Dainippon Inkie Corp.), Epi Coat 871, copper 872 (above, Japan Epoxy Resin Co., Ltd.), ED-5661, copper 5566 (above, Celanese coating company);

Examples of the aliphatic polyglycidyl ethers include EPOLITE 100MF (Kyoeisha Chemical Co., Ltd.), Epiol TMP ((Nihon Yushi Co., Ltd.)), and the like.

It is preferable that an epoxy compound (A) is a polymer, and it is more preferable that it is a polymer which has a carboxyl group further. Moreover, it is preferable that the polymer as an [A] epoxy compound is alkali-soluble resin which has solubility in the image development process process, The copolymer which has a carboxyl group containing structural unit and an epoxy group containing structural unit (Hereinafter, "[A] copolymer) It is more preferable from the viewpoint of the solubility with respect to alkaline developing solution, the obtained coloring pattern, and the hardness of a color filter.

As a method of synthesizing a copolymer having a carboxyl group-containing structural unit and an epoxy group-containing structural unit, for example, (a1) unsaturated carboxylic acid and / or unsaturated to give a carboxyl group-containing structural unit (the carboxyl group also includes an acid anhydride group). A carbonic anhydride (hereinafter also referred to as "(a1) compound") and a radically polymerizable compound (hereinafter also referred to as "(a2) compound") having an epoxy group to impart an epoxy group-containing structural unit (hereinafter referred to as "a compound)" in a solvent It is obtained by copolymerizing using. Moreover, as needed (a3) compound, radically polymerizable compounds, such as alkyl ester of (meth) acrylic acid, may be contained together with (a1) compound and (a2) compound, and may be copolymerized.

As the compound (a1), for example,

Acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid Monocarboxylic acids such as;

Dicarboxylic acids such as maleic acid, fumaric acid and citraconic acid;

And dicarboxylic acid anhydrides such as maleic anhydride.

Among these (a1) compounds, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and solubility in an alkaline developer.

(a1) A compound can be used individually or in combination of 2 or more types. As the usage-amount of the (a1) compound in the synthesis | combination of (A) copolymer, 5 mass%-40 mass% are preferable with respect to 100 mass% of all the monomers used, 7 mass%-30 mass% are more preferable, 8 mass%-25 mass% are especially preferable. By setting the usage-amount of the compound (a1) to 5% by mass to 40% by mass, a coloring composition in which the properties such as radiation sensitivity and storage stability are optimized to a higher level can be obtained.

As a (a2) compound, the radically polymerizable compound which has an oxiranyl group, the radically polymerizable compound which has an oxetanyl group, etc. are mentioned, for example.

As a radically polymerizable compound which has an oxiranyl group, for example

Acrylic acid such as glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxy cyclohexyl methyl acrylate Epoxy alkyl esters;

Glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, methacrylic acid Methacrylic acid epoxy alkyl esters such as acid 3,4-epoxycyclohexylmethyl;

α-alkylacrylic acid epoxyalkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl and α-ethyl acrylate 6,7-epoxyheptyl;

and glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether.

As a radically polymerizable compound which has an oxetanyl group, for example, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacrylo) Yloxymethyl) -2-methyloxetane, 3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryl Loyloxyethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methylox Cetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (acryloyloxyethyl) oxetane, 2- (meta Chryloyloxymethyl) oxetane, 2-methyl-2- (methacryloyloxymethyl) oxetane, 3-methyl-2- (methacryloyloxymethyl) oxetane, 4-methyl-2- ( Methacryloyloxymethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- ( Tacryloyloxyethyl) -2-methyloxetane, 2- (methacryloyloxyethyl) -4-methyloxetane, 2- (acryloyloxymethyl) oxetane, 2-methyl-2- (acrylic Loyloxymethyl) oxetane, 3-methyl-2- (acryloyloxymethyl) oxetane, 4-methyl-2- (acryloyloxymethyl) oxetane, 2- (2- (2-methyljade Cetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (acryloyloxyethyl) -2-methyloxetane, 2- (acryloyl (Meth) acrylic acid ester, such as oxyethyl) -4-methyloxetane, is mentioned.

Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3, 4-epoxybutyl, 3- (acryloyloxymethyl) oxetane, and 3- (methacryloyloxy) Adhesiveness with respect to the board | substrate of the coloring pattern and color filter from which methyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane and 2- (methacryloyloxymethyl) oxetane are obtained is excellent, and it is excellent It is preferable at the point which has heat resistance and improves the reliability in a display element.

Compounds (a2) may be used alone or in combination of two or more. As the usage-amount of the (a2) compound in the synthesis | combination of (A) copolymer, 10 mass%-70 mass% are preferable with respect to 100 mass% of all monomers to be used. By setting the usage-amount of a compound (a2) to 10 mass%-70 mass%, the control of the molecular weight of a [A] copolymer becomes easy, and the coloring composition optimized to a higher level with a sensitivity etc. is obtained.

(a3) The compound is (meth) acrylic acid alkyl ester, (meth) acrylic acid alicyclic ester, unsaturated hetero 5- and 6-membered ring (meth) acrylic acid ester containing an oxygen atom, hydroxyalkyl ester of (meth) acrylic acid, (meth) ) Acrylic acid aryl ester, maleimide compound, styrene, (alpha) -methylstyrene, and at least 1 sort (s) of radically polymerizable compound chosen from the group which consists of 1, 3- butadiene.

As (meth) acrylic-acid alkylester, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, etc. are mentioned, for example. have.

Examples of the (meth) acrylic acid alicyclic alkyl esters include (meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-2-methylcyclohexyl, and (meth) acrylic acid tricyclo [5.2.1.0 ^{2, 6} ] decane-8-yl, isobornyl (meth) acrylate, and the like.

As a (meth) acrylic acid ester which has a complex 5 and 6 membered ring containing an oxygen atom, it is, for example

Containing tetrahydrofuran skeletons such as tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxypropionate tetrahydrofurfuryl ester, and 3- (meth) acryloyloxytetrahydrofuran-2-one Meta) acrylic acid ester;

2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan-2- Butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-ene-3 (Meth) acrylic acid containing furan skeletons such as -one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, and 6- (2-furyl) -6-methyl-1-hepten-3-one ester;

(Tetrahydropyran-2-yl) methylmethacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -octo-1-en-3-one, 2-methacrylic acid tetrahydro (Meth) acrylic acid esters containing tetrahydropyran skeletons such as pyran-2-yl ester and 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one;

4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1,5-dioxa-6-oxo-7-octenyl) -6- (Meth) acrylic acid ester containing pyran skeletons, such as methyl-2-pyran, etc. are mentioned.

As hydroxyalkyl ester of (meth) acrylic acid, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2, for example And 3-dihydroxypropyl.

As (meth) acrylic-acid aryl ester, (meth) acrylic-acid phenyl, (meth) acrylic-acid benzyl, etc. are mentioned, for example.

As the maleimide compound, for example, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzyl maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide pro Cypionate, N- (9-acridinyl) maleimide, etc. are mentioned.

Compounds (a3) may be used alone or in combination of two or more. As the usage-amount of the (a3) compound in the synthesis | combination of (A) copolymer, 10 mass%-70 mass% are preferable with respect to 100 mass% of all the monomers used, and 15 mass%-65 mass% are more preferable. . By setting the amount of the compound (a3) to 10% by mass to 70% by mass, the control of the molecular weight of the copolymer becomes easy, and a coloring composition optimized to a higher level of sensitivity and the like is obtained.

As a synthesis | combining method of the [A] copolymer, the method of superposing | polymerizing (a1) compound, (a2) compound, (a3) compound using a radical polymerization initiator in a solvent, etc. are mentioned, for example.

As a radical polymerization initiator, although it selects suitably according to the kind of polymerizable unsaturated compound used, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvalero Nitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'- Azo compounds, such as azobis (2-methyl propionate) and 2,2'- azobis (4-methoxy-2, 4- dimethylvaleronitrile), etc. are mentioned. Among these radical polymerization initiators, 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) are preferable. A radical polymerization initiator can use individual or 2 types or more.

In the said polymerization, as a usage-amount of a radical polymerization initiator, 0.1 mass%-50 mass%, 0.1 mass%-20 mass% are preferable normally with respect to 100 mass% of polymerizable unsaturated compounds.

In addition, in the superposition | polymerization of [A] copolymer, a molecular weight modifier can be used. As a molecular weight modifier, for example

Halogenated hydrocarbons such as chloroform and carbon tetrabromide;

mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid;

Xanthogens, such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide;

Terpinolene, (alpha) -methylstyrene dimer, etc. are mentioned.

As the usage-amount of a molecular weight control agent, 0.1 mass%-50 mass%, 0.2 mass%-16 mass% are preferable normally with respect to 100 mass% of total of (a1) compound, (a2) compound, and (a3) compound, 0.4 Mass%-8 mass% are more preferable.

As polymerization temperature, 0 degreeC-150 degreeC and 50 degreeC-120 degreeC are preferable normally. As polymerization time, 10 minutes-20 hours, 30 minutes-6 hours are preferable normally.

As polystyrene conversion weight average molecular weight (Mw) of the copolymer (A), 2x10 <^3> -1 * 10 <^5> is preferable and 5x10 <^3> -5 * 10 <^4> is more preferable. By making Mw of a copolymer into the said specific range, while obtaining sufficient image development margin of a coloring composition, the fall of the residual film ratio (the ratio which a pattern-shaped thin film remain | survives appropriately) of the formed coating film is prevented, and also It becomes possible to maintain the shape, heat resistance, etc. of the color pattern obtained favorably. In addition, a good pattern shape can be obtained by maintaining a high radiation sensitivity.

As molecular weight distribution (Mw / Mn) of the [A] copolymer, 5.0 or less are preferable and 3.0 or less are more preferable. By setting Mw / Mn of the copolymer [A] to 5.0 or less, the pattern shape of the color pattern obtained can be kept favorable. Since the coloring composition containing the [A] copolymer which has Mw and Mw / Mn of such a preferable range has high image development resistance, in the image development process, a predetermined pattern shape is formed easily, without generating image development residue. can do.

In addition, the weight average molecular weight (Mw) in this specification was measured by the gel permeation chromatography (GPC) under the following apparatus and conditions.

Device: GPC-101 (Showa Denko KK)

Column: combine GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran

Examples of the solvent used for the polymerization reaction for producing the copolymer (A) include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol mono Alkyl ether acetate, a propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, other ester, etc. are mentioned.

Examples of the alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.

Examples of the ethers include cyclic ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl ether propionates. have.

As cyclic ether, tetrahydrofuran etc. are mentioned, for example.

As glycol ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. are mentioned, for example.

As ethylene glycol alkyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc. are mentioned, for example.

As diethylene glycol alkyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc. are mentioned, for example.

As propylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc. are mentioned, for example.

As propylene glycol monoalkyl ether acetate, a propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, a propylene glycol monopropyl ether acetate, a propylene glycol monobutyl ether acetate etc. are mentioned, for example.

Examples of the propylene glycol monoalkyl ether propionate include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, and the like. Can be mentioned.

As aromatic hydrocarbons, toluene, xylene, etc. are mentioned, for example.

As ketones, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanone, etc. are mentioned, for example.

As other esters, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, and hydroxy Methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid butyl, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionic acid propyl, 3-hydroxy Butyl oxypropionate, methyl 2-hydroxy-3-methylbutanoic acid, methyl methoxyacetic acid, ethyl methoxyacetic acid, methoxyacetic acid propyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, ethoxyacetic acid propyl Butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propoxyacetate Acid propyl, butyl propoxyacetic acid, methyl butoxyacetic acid, ethyl butoxyacetic acid, butyl butoxyacetic acid, butyl butoxyacetic acid, 2-methoxypropionate, ethyl 2-methoxypropionic acid, 2-methoxypropionic acid propyl, 2 Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2- Propyl butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionic acid, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-E Ethyl oxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Butyl, 3-propoxy propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like.

<[B] coloring agent>

The coloring agent (B) is not particularly limited as long as it has coloring properties, and color and material can be appropriately selected according to the use of the coloring pattern and the color filter. As the colorant, any of pigments, dyes and natural dyes can be used, for example, but since the color pattern and color filter require high color purity, brightness, contrast and the like, pigments and / or dyes are preferred, and dyes are More preferred.

As said pigment, any of an organic pigment and an inorganic pigment may be sufficient, and as an organic pigment, the compound classified by the pigment in a color index (C.I .; The "Society" of "Dyers" and "Colourists") is mentioned, for example. Specifically, what is attached to the following color index (C.I.) names is mentioned.

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

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

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

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

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

C.I. Pigment green 7, east 36, east 58;

C.I. Pigment brown 23, east 25;

C.I. Pigment black 1, copper 7, etc. are mentioned.

Examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, bengala (red iron oxide (III)), cadmium red, ultramarine blue, Blue wire, chromium oxide rust, cobalt rust, umber, titanium black, synthetic iron black, carbon black, etc. are mentioned.

Examples of the chemical structure of the dye include triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran and indigo. Can be mentioned. Among these, dyes of a pyrazole azo system, an anilino azo system, a pyrazolotriazole azo system, a pyridone azo system, an anthraquinone system and an anthrapyridone system are preferable.

As the colorant (B), known dyes which are soluble in organic solvents can be used, and examples thereof include oil-soluble dyes, acid dyes or derivatives thereof, direct dyes, modern dyes, and the like.

C.I. As the oil-soluble dye, for example

C.I. Solvent yellow 4, east 14, east 15, east 23, east 24, east 38, east 62, east 63, east 68, east 82, east 88, east 94, east 98, east 99, east 162, east 179;

C.I. Solvent red 45, copper 49, copper 125, copper 130;

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

C.I. Solvent blue 35, east 37, east 59, east 67;

C.I. Solvent green 1, 3, 4, 5, 5, 7, 28, 29, 32, 33, 34, 35, and the like.

C.I. As an acid dye, for example

C.I. Acid Yellow 1, East 3, East 7, East 9, East 11, East 17, East 23, East 25, East 29, East 34, East 36, East 38, East 40, East 42, East 54, East 65, East 72, East 73, East 76, East 79, East 98, East 99, East 111, East 112, East 113, East 114, East 116, East 119, East 123, East 128, East 134, East 135, East 138, East 139, East 140, East 144, East 150, East 155, East 157, East 160, East 161, East 163, East 168, East 169, East 172, East 177, East 178, East 179, East 184, East 190 , East 193, East 196, East 197, East 199, East 202, East 203, East 204, East 205, East 207, East 212, East 214, East 220, East 221, East 228, East 230, East 232, East 235, East 238, East 240, East 242, East 243, East 251;

Valifast yellow 1101, East 1109, East 1151, East 3108, East 3120, East 3130, East 3150, East 3170, East 4120;

C.I. Acid Red 1, East 4, East 8, East 14, East 17, East 18, East 26, East 27, East 29, East 31, East 34, East 35, East 37, East 42, East 44, East 50, East 51, East 52, East 57, East 66, East 73, East 80, East 87, East 88, East 91, East 92, East 94, East 97, East 103, East 111, East 114, East 129, East 133, East 134, East 138, East 143, East 145, East 150, East 151, East 158, East 176, East 182, East 183, East 198, East 206, East 211, East 215, East 216, East 217, East 227 , East 228, East 249, East 252, East 257, East 258, East 260, East 261, East 266, East 268, East 270, East 274, East 277, East 280, East 281, East 195, East 308, East 312, East 315, East 316, East 339, East 341, East 345, East 346, East 349, East 382, East 383, East 394, East 401, East 412, East 417, East 418, East 422, East 426;

C.I. Acid Orange 6, East 7, East 8, East 10, East 12, East 26, East 50, East 51, East 52, East 56, East 62, East 63, East 64, East 74, East 75, East 94, East 95, 107, 108, 169, 173;

C.I. Acid Blue 1, East 7, East 9, East 15, East 18, East 23, East 25, East 27, East 29, East 40, East 42, East 45, East 51, East 62, East 70, East 74, East 80, East 83, East 86, East 87, East 90, East 92, East 96, East 103, East 108, East 112, East 113, East 120, East 129, East 138, East 147, East 150, East 158, East 171, East 182, East 192, East 210, East 242, East 249, East 243, East 256, East 259, East 267, East 278, East 280, East 285, East 290, East 296, East 315, East 324 , 335, 340;

C.I. Acid violet 6B, copper 7, copper 9, copper 17, copper 19, copper 49;

C.I. Acid green 1, east 3, east 5, east 9, east 16, east 25, east 27, east 50, east 58, east 63, east 65, east 80, east 104, east 105, east 106, east 109;

C.I. And dyes such as acid black 24.

C.I. As a direct dye, for example

C.I. Direct Yellow 2, East 33, East 34, East 35, East 38, East 39, East 43, East 47, East 50, East 54, East 58, East 68, East 69, East 70, East 71, East 86, East 93, 94, 94, 98, 102, 108, 109, 129, 136, 138, 141;

C.I. Direct Red 79, East 82, East 83, East 84, East 91, East 92, East 96, East 97, East 98, East 99, East 105, East 106, East 107, East 172, East 173, East 176, East 177, East 179, East 181, East 182, East 184, East 204, East 207, East 211, East 213, East 218, East 220, East 221, East 222, East 232, East 233, East 234, East 241, East 243, east 246, east 250;

C.I. Direct Orange 34, East 39, East 41, East 46, East 50, East 52, East 56, East 57, East 61, East 64, East 65, East 68, East 70, East 96, East 97, East 106, East 107;

C.I. Direct Blue 57, East 77, East 80, East 81, East 84, East 85, East 86, East 90, East 93, East 94, East 95, East 97, East 98, East 99, East 100, East 101, East 106, East 107, East 108, East 109, East 113, East 114, East 115, East 117, East 119, East 137, East 149, East 150, East 153, East 155, East 156, East 158, East 159, East 160, East 161, East 162, East 163, East 164, East 166, East 167, East 170, East 171, East 172, East 173, East 188, East 189, East 190, East 192, East 193, East 194 , East 196, East 198, East 199, East 200, East 207, East 209, East 210, East 212, East 213, East 214, East 222, East 228, East 229, East 237, East 238, East 242, East 243, East 244, East 245, East 247, East 248, East 250, East 251, East 252, East 256, East 257, East 259, East 260, East 268, East 274, East 275, East 293;

C.I. Direct Violet 47, East 52, East 54, East 59, East 60, East 65, East 66, East 79, East 80, East 81, East 82, East 84, East 89, East 90, East 93, East 95, East 96, 103, 104;

C.I. Direct Green 25, East 27, East 31, East 32, East 34, East 37, East 63, East 65, East 66, East 67, East 68, East 69, East 72, East 77, East 79, East 82, etc. Can be mentioned.

C.I. As a modern dye, for example

C.I. Modern yellow 5, east 8, east 10, east 16, east 20, east 26, east 30, east 31, east 33, east 42, east 43, east 45, east 56, east 61, east 62, east 65;

C.I. Modern Red 1, East 2, East 3, East 4, East 9, East 11, East 12, East 14, East 17, East 18, East 19, East 22, East 23, East 24, East 25, East 26, East 30, East 32, East 33, East 36, East 37, East 38, East 39, East 41, East 43, East 45, East 46, East 48, East 53, East 56, East 63, East 71, East 74 , 85, 86, 88, 90, 94, 95;

C.I. Modern Orange 3, East 4, East 5, East 8, East 12, East 13, East 14, East 20, East 21, East 23, East 24, East 28, East 29, East 32, East 34, East 35, East 36, East 37, East 42, East 43, East 47, East 48;

C.I. Modern Blue 1, East 2, East 3, East 7, East 8, East 9, East 12, East 13, East 15, East 16, East 19, East 20, East 21, East 22, East 23, East 24, East 26, east 30, east 31, east 32, east 39, east 40, east 41, east 43, east 44, east 48, east 49, east 53, east 61, east 74, east 77, east 83, east 84 ;

C.I. Modern Violet 1, East 2, East 4, East 5, East 7, East 14, East 22, East 24, East 30, East 31, East 32, East 37, East 40, East 41, East 44, East 45, East 47, east 48, east 53, east 58;

C.I. Modern Green 1, East 3, East 4, East 5, East 10, East 15, East 19, East 26, East 29, East 33, East 34, East 35, East 41, East 43, East 53, etc. have.

As content of the (B) coloring agent, 1 mass part-400 mass parts are preferable with respect to 100 mass parts of [A] epoxy compounds, and 1 mass part-300 mass parts are more preferable. By adjusting the content of the colorant to 1 part by mass to 400 parts by mass, the alkali developability of the coloring composition, the heat resistance of the pixel, the solvent resistance, the color pattern, and the high brightness and high contrast as the color filter can be achieved in a good balance. have.

<[C] compound>

The compound [C] is not particularly limited as long as it is a compound having a hydroxyl group or a carboxyl group. As the compound [C], a compound capable of encapsulating the [D] amine compound is preferable, and the group consisting of the compounds represented by the following formulas (1) and (2), respectively, from the viewpoint of suitably forming the inclusion compound described later. It is preferable that it is at least 1 sort (s) of compound chosen from.

In said formula (1), X is a single bond, a methylene group, or a C2-C6 alkylene group. R ^{1 to} R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, or a phenyl group which may have a substituent. In said formula (2), R <^9> is a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, or a hydroxyl group.

As a C2-C6 alkylene group represented by said X, an ethylene group, a propylene group, etc. are mentioned, for example. As a C1-C12 alkyl group represented by said R <^1> -R <^8> and R <^9> , a methyl group, an ethyl group, a propyl group, a butyl group, etc. are mentioned, for example. As a C1-C12 alkoxy group represented by said R <^1> -R <^8> and R <^9> , a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example.

It is preferable that the compound represented by said formula (1) is a compound represented by said formula (1-1). By making the compound represented by the said Formula (1) into a tetrakisphenol type compound with higher symmetry represented by said Formula (1-1), it is considered that the clathrate improves more, and as a result, storage stability improves further and it is low temperature. Hardening in can also be accelerated.

As a tetrakisphenol compound represented by said formula (1-1), it is 1,1,2,2- tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2- tetrakis (3- Methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro- 4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dichloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-bromo-4 -Hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dibromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-t-butyl 4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3 -Fluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-difluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis ( 3-methoxy-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) ethane, 1,1,2,2-te Thrakis (3-chloro-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-bromo-5-methyl-4-hydroxyphenyl) ethane, 1,1 , 2,2-tetrakis (3-methoxy-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-t-butyl-5-methyl-4-hydroxy Phenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-bromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-phenyl 4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-phenyl-4-hydroxyphenyl) ethane, 1,1,3,3-tetrakis (4-hydroxyphenyl) propane , 1,1,3,3-tetrakis (3-methyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dimethyl-4-hydroxyphenyl) propane, 1 , 1,3,3-tetrakis (3-chloro-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dichloro-4-hydroxyphenyl) propane, 1,1 , 3,3-tetrakis (3-bromo-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dibromo-4-hydroxyphenyl Propane, 1,1,3,3-tetrakis (3-phenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-diphenyl-4-hydroxyphenyl) Propane, 1,1,3,3-tetrakis (3-methoxy-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) Propane, 1,1,3,3-tetrakis (3-t-butyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-di-t-butyl-4- Hydroxyphenyl) propane, 1,1,4,4-tetrakis (4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methyl-4-hydroxyphenyl) butane, 1, 1,4,4-tetrakis (3,5-dimethyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-chloro-4-hydroxyphenyl) butane, 1,1, 4,4-tetrakis (3,5-dichloro-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methoxy-4-hydroxyphenyl) butane, 1,1,4 , 4-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-bromo-4-hydroxyphenyl) butane, 1,1,4 , 4-tele Lakis (3,5-dibromo-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-t-butyl-4-hydroxyphenyl) butane, 1,1,4,4 -Tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) butane and the like.

Among these, when the clathrate compound mentioned later is formed, 1,1,2,2- tetrakis (the said coloring composition is more excellent in storage stability at room temperature, and a hardening accelerator is easy to be released at the time of heating. 4-hydroxyphenyl) ethane is preferred.

As a compound represented by the said Formula (2), for example, 5-nitroisophthalic acid, 5-hydroxyisophthalic acid, 5-methylisophthalic acid, 5-methoxyisophthalic acid, 4-nitroisophthalic acid, 4-hydroxyiso Phthalic acid, 4-methylisophthalic acid, 4-methoxyisophthalic acid, and the like. Among these, 5-nitroisophthalic acid and 5-hydroxyisophthalic acid are preferable.

The compound [C] can be used alone or in combination of two or more thereof. As content of the [C] compound in the said coloring composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] epoxy compounds, 0.2 mass part-5 mass parts are more preferable, and it mentions later D] It is preferable to set it as about 1 time-about 2 time with respect to an amine compound.

<[D] amine compound>

Although it does not specifically limit as [D] amine compound, It is preferable that it is an amine compound which can be included in [C] compound, and it is more preferable that it is an imidazole compound or a benzoimidazole compound. Among these, since an imidazole compound is easy to be included in [C] compound, the storage stability at room temperature of the said coloring composition improves. Moreover, since an imidazole compound is excellent in reactivity with an epoxy group, it contributes to low temperature hardening of 200 degrees C or less.

As an imidazole compound, the compound etc. which are represented by following formula (3) are mentioned, for example.

(In formula (3), R <^10> -R <^13> respectively independently represents a hydrogen atom, a C1-C6 alkyl group, a naphthyl group, an anthryl group, a phenanthryl group, a 9-fluorenyl group, a halogen atom, and C1-C1. A phenyl group which may be substituted with an alkyl group, a phenyl group, or a halogen atom.

As an imidazole compound, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imid Dazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H -Imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4 -Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6- [2'-methylimidazolyl -(1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-ethyl-4-imidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-Ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanur Acid adducts, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5 -Di (2-cyanoethoxy) methylimidazole, 1-benzyl-2-phenylimidazolium trimellitate, and the like.

Among them, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-methylimidazole, and 2-ethyl-4-methylimidazole which have high reactivity and excellent in inclusion stability are preferred.

It is preferable that the said imidazole compound has 1 or more of C1-C6 substituents. Since such imidazole compound is stably contained, it does not adversely affect the storage stability of the said coloring composition, and since steric hindrance is small, it is excellent in reactivity and can exhibit low temperature hardening property when clathrate collapses.

As an imidazole compound which has 1 or more of said C1-C6 substituents, it is, for example

Imidazole compounds having one substituent of 1 to 6 carbon atoms, such as 2-methylimidazole and 2-phenylimidazole;

Imidazoles having two substituents of 1 to 6 carbon atoms, such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and 2-phenyl-4-methyl-5-hydroxy methylimidazole Compounds and the like.

As a benzimidazole compound, the compound etc. which are represented by following formula (4) are mentioned, for example.

(In formula (4), R <^14> -R <^16> is a hydrogen atom, a C1-C6 alkyl group, a naphthyl group, an anthryl group, a phenanthryl group, a 9-fluorenyl group, a halogen atom, C1 each independently, It is a phenyl group which may be substituted by the alkyl group, the phenyl group, or a halogen atom of -6.m is an integer of 0-4. However, when R <^14> is several, some R <^14> may be same or different).

As a benzoimidazole compound, for example, 2-methylbenzoimidazole, 4-methylbenzoimidazole, 5-methylbenzoimidazole, 6-methylbenzoimidazole, 7-methylbenzoimidazole, 2-methyl-6- Methylbenzoimidazole, 2-methyl-5-methylbenzoimidazole, 2-ethyl-6-methylbenzoimidazole, 2-methyl-6-ethylbenzoimidazole, 2-ethyl-5-methylbenzoimidazole, 2 -Methyl-5-ethylbenzoimidazole etc. are mentioned.

Among them, 2-methylbenzoimidazole, 2-methyl-6-methylbenzoimidazole, and 2-methyl-5-methylbenzoimidazole are selected from the viewpoint of achieving a high level of storage stability and curing promotion of the composition. desirable.

It is preferable that the said benzimidazole compound has 1 or more of C1-C6 substituents. Since such imidazole compound is stably contained, it does not adversely affect the storage stability of the said coloring composition, and since steric hindrance is small, it is excellent in reactivity and can exhibit low temperature hardening property when clathrate collapses.

As a benzoimidazole compound which has one or more said C1-C6 substituents, For example, the benzoimidazole compound which has one C1-C6 substituents, such as 2-methylbenzoimidazole; And a benzoimidazole compound having two substituents of 1 to 6 carbon atoms, such as 2-methyl-6-methylbenzoimidazole and 2-methyl-5-methylbenzoimidazole.

The amine compound [D] can be used alone or in combination of two or more thereof. As content of the [D] amine compound in the said coloring composition, 0.05 mass part-5 mass parts are preferable with respect to 100 mass parts of [A] epoxy compounds, 0.1 mass part-2.5 mass parts are more preferable, and [C ] It is preferable to set it as about 0.5 times-1 time with respect to a compound.

<Clathrate compound>

In the said coloring composition, it is preferable that at least one part of [D] amine compound is included in [C] compound. In the coloring composition, at least a part of the amine compound [D] is included in the [C] compound to form a clathrate compound, thereby achieving both storage stability and low temperature baking.

The method for inclusion of the [D] amine compound with the [C] compound is not particularly limited, and examples thereof include the method described in JP-A-11-071449. The said coloring composition whose viscosity in 25 degreeC is 1.0 mPa * s or more and 50 mPa * s or less mix | blends the clathrate compound which the [D] amine compound contained in the [C] compound with [A] epoxy compound, and [B] colorant, It is preferable to prepare. According to the said process, the said coloring composition containing a clathrate compound can be manufactured efficiently.

When forming a clathrate compound in advance and containing it in the said coloring composition, as content of the clathrate compound in the said coloring composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] epoxy compounds, and 0.2 mass 5 mass parts is more preferable. By making content of a clathrate compound into 0.1 mass part-10 mass parts, the storage stability of the said coloring composition and hardening acceleration of a cured film can be made compatible at a high level.

<[E] polymeric compound>

It is preferable that the said coloring composition contains the [E] polymerizable compound further. As the coloring composition further contains the [E] polymerizable compound, even in the case of low exposure amount, the color which was more excellent in heat resistance, solvent resistance, etc. A filter is obtained.

The polymerizable compound (E) is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond. For example,? -Carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylic Latene, bisphenoxyethanol fluorenedi (meth) acrylate, dimethylol tricyclodecanedi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- ( 2'-vinyloxyethoxy) ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Other (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, succinic acid modified penta In addition to erythritol tri (meth) acrylate and the like, a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, one or more hydroxyl groups in a molecule, and three to five (meth) acryloyl jades And urethane (meth) acrylate compounds obtained by reacting a compound having a timing.

As a commercial item of the [E] polymerizable compound, for example,

ARONIX M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, M-7100, M-8030, M M-8060, M-8100, M-8530, M-8560, M-9050, ARONIX TO-1450, TO-1382, TO-756 (above, Toagose Co., Ltd.), KAYARAD DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120, copper MAX-3510 (above, Nippon Kayaku Co., Ltd.), biscotti (VISCOAT) 295, copper 300, copper 360, As GPT, copper 3PA, copper 400 (above, Osaka Yukikagaku Kogyo Co., Ltd.), urethane acrylate compound, NEW FRONTIER R-1150 (Daiichi Kogyo Seyaku Co., Ltd.), KAYARAD 'DPHA-40H , UX-5000 (above, Nippon Kayaku Co., Ltd.), UN-9000H (Negami Kogyo Co., Ltd.), Aronix M-5300, East M-5600, East M-5700, M-210, East M- 220, East M-240, East M-270, East M-6200, East M-305, East M-309, East M-310, East M-315 (above, Toagosei Co., Ltd.), KAYARAD HDDA, KA YARAD'HX-220, HX-620, R-526, R-167, R-604, R-684, R-551, R-712, UX-2201, UX-2301, UX- 3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, Nippon Kayaku Co., Ltd.), Atresin (ARTRESIN) UN-9000PEP, East UN-9200A, East UN-7600, East UN-333, East UN-1003, East UN-1255, East UN-6060PTM, East UN-6060P (above, Negamiko Bridge Co., Ltd.), SH And -500B Biscot 260, 312, and 335HP (above, Osaka Yukikagaku Kogyo Co., Ltd.).

[E] The polymerizable compound may be used alone or in combination of two or more thereof. As a usage-amount of the [E] polymeric compound in the said coloring composition, 1 mass part-490 mass parts are preferable with respect to 100 mass parts of [A] epoxy compounds, and 20 mass parts-300 mass parts are more preferable. By containing [E] polymeric compound in such an amount of use, the said coloring composition can form the coloring pattern and color filter which have sufficient heat resistance, solvent resistance, and voltage hold ratio even in low exposure amount. When the usage-amount of a polymerizable compound (E) is 500 mass parts or more, the unbaking ethylenically unsaturated group which does not participate in a polymerization reaction in a film | membrane increases in the postbaking temperature of 200 degrees C or less. For this reason, at the time of heating, since unreacted ethylenically unsaturated group advances thermal polymerization further, hardening shrinkage advances more than design film thickness. When the change in the film thickness becomes large before and after heating, the color change of the coloring pattern increases, and the color uniformity tends to decrease.

<[F] radiation sensitive polymerization initiator>

It is preferable that the said coloring composition further contains a [F] radiation sensitive polymerization initiator. The coloring composition further contains a radiation sensitive polymerization initiator [F] to obtain a coloring pattern and a color filter which are more excellent in heat resistance, solvent resistance, and the like even in the case of a low exposure amount.

[F] radiation sensitive polymerization initiator contained in the coloring composition of this invention is a component which produces the active species which can start superposition | polymerization of a [E] polymeric compound in response to radiation. As such a [F] radiation sensitive polymerization initiator, an O-acyl oxime compound and an acetophenone compound are preferable.

Examples of the O-acyl oxime compound include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone-1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1- Onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane-1-onoxime-O-benzoate, 1- [9- n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2- Methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetra Hydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -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) etc. are mentioned. All.

Among these O-acyl oxime compounds, 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone-1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl)- 9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-diox Solanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

As an acetophenone compound, the (alpha)-amino ketone compound, the (alpha)-hydroxy ketone compound, etc. are mentioned, for example.

As an α-amino ketone compound, for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl)- 1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, etc. are mentioned. .

As an α-hydroxy ketone compound, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1 -One, 4- (2-hydroxy ethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like.

Of these acetophenone compounds, α-aminoketone compounds are preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4 More preferred is -methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one.

[F] The radiation sensitive polymerization initiator may be used alone or in combination of two or more thereof. As a usage-amount of a [F] radiation sensitive polymerization initiator, 1 mass part-40 mass parts are preferable with respect to 100 mass parts of [A] epoxy compounds, and 5 mass parts-30 mass parts are more preferable. By setting the usage-amount of the [F] radiation sensitive polymerization initiator to 1 mass part-40 mass parts, the said coloring composition can form the coloring pattern and color filter which have a high hardness etc. even in the case of low exposure amount.

<Other optional components>

The coloring composition is desired in addition to the above-mentioned [A] epoxy compound, [B] colorant, [C] compound, [D] amine compound, [E] polymerizable compound as a suitable component and [F] radiation sensitive polymerization initiator. As needed, other [G] adhesion | attachment adjuvant, [H] surfactant, [I] storage stabilizer, [J] heat resistance improver, etc. can be contained as needed of other arbitrary components in the range which does not impair the effect to make. These other arbitrary components may be used independently and may use 2 or more types. Hereinafter, each component is explained in full detail.

[[G] Adhesion Aids]

The adhesive aid [G] can be used in order to improve the adhesiveness of the coloring pattern and color filter which are obtained, and a board | substrate further. [G] As the adhesion assistant, functional silane coupling agents having reactive functional groups such as carboxyl group, methacryloyl group, vinyl group, isocyanate group and oxiranyl group are preferable, and for example, trimethoxysilylbenzoic acid and γ- Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclo Hexyl) ethyl trimethoxysilane etc. are mentioned.

As the usage-amount of the [G] adhesion | attachment adjuvant, 20 mass parts or less are preferable with respect to 100 mass parts of [A] epoxy compounds, and 15 mass parts or less are more preferable. When the usage-amount of the [G] adhesion | attachment adjuvant exceeds 20 mass parts, there exists a tendency which tends to generate image development residue.

[[H] Surfactant]

[H] Surfactant can be used in order to improve the coating film formability of a coloring composition further. Examples of the [H] surfactant include fluorine-based surfactants, silicone-based surfactants, and other surfactants.

As a fluorine type surfactant, the compound which has a fluoroalkyl group and / or a fluoroalkylene group in at least any part of a terminal, a main chain, and a side chain is preferable, For example, 1,1,2,2- tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1, 2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1, 2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycoldi (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro-n-dodecanesulfonic acid Sodium, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane Or sodium fluoroalkylbenzenesulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkyl carbonate, diglycerin tetrakis (fluoroalkylpol Reoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxy ethanol, perfluoroalkyl alkoxylate, carboxylic acid fluoroalkyl ester Etc. can be mentioned.

As a commercial item of a fluorine-type surfactant, BM-1000, BM-1100 (above, BM'CHEMIE company), Megapack (MEGAFAC) F142D, copper 172, copper 173, copper 183, copper 178, copper 191, copper 471, East 476 (above, Dai Nippon Inkaki Kagaku Kogyo Co., Ltd.), Fluorad (FLUORAD) FC-170C, East 171, East 430, East 431 (above, Sumitomo 3M Kabuki Kaisha), SURFLON S- 112, East 113, East 131, East 141, East 145, East 382, Suplon SC-101, East 102, East 103, East 104, East 105, East 106 (above, Asahi Glass Co., Ltd.), F-Top (EFTOP) EF301, East 303, East 352 (above, Shin Akita Kasei Co., Ltd.), FTERGENT FT-100, East 110, East 140A, East 150, East 250, East 251, East 300, East 310 , Copper 400S, aftergent FTX-218, copper 251 (above, neos).

As a commercial item of a silicone type surfactant, for example, Toray silicon (TORAY SILICON) DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032 , SF-8428, DC-57, DC-190 (above, Dow Corning Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF -4452 (above, GE Toshiba Silicone Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.), etc. are mentioned.

As other surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene-n-octylphenyl ether and polyoxyethylene-n-nonylphenyl ether; Nonionic surfactant, such as polyoxyethylene dialkyl ester, such as polyoxyethylene dilaurate and polyoxyethylene distearate, (meth) acrylic-acid copolymer polyflow (POLYFLOW) No.57, copper NO.95 ( The Kyoeisha Chemicals Co., Ltd. is mentioned above.

As the usage-amount of [H] surfactant, 1.0 mass part or less is preferable with respect to 100 mass parts of [A] epoxy compounds, and 0.7 mass part or less is more preferable. When the usage-amount of [H] surfactant exceeds 1.0 mass part, it will become easy to produce a film nonuniformity.

[[I] preservation stabilizer]

[I] Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds and the like, and more specifically 4-methoxyphenol and N-nitroso -N-phenylhydroxylamine aluminum etc. are mentioned.

As the usage-amount of [I] storage stabilizer, 3.0 mass parts or less are preferable with respect to 100 mass parts of [A] epoxy compounds, and 0.5 mass parts or less are more preferable. When the compounding quantity of [I] storage stabilizer exceeds 3.0 mass parts, a sensitivity may fall and a pattern shape may deteriorate.

[[J] Heat Resistance Enhancer]

[J] As the heat resistance improving agent, for example, an N- (alkoxymethyl) glycoluril compound, an N- (alkoxymethyl) melamine compound, etc. may be mentioned.

Examples of the N- (alkoxymethyl) glycoluril compound include N, N, N ', N'-tetra (methoxymethyl) glycoluril, N, N, N', N'-tetra (ethoxymethyl) glycol Uryl, N, N, N ', N'-tetra (n-propoxymethyl) glycoluril, N, N, N', N'-tetra (i-propoxymethyl) glycoluril, N, N, N ' , N'-tetra (n-butoxymethyl) glycoluril, N, N, N ', N'-tetra (t-butoxymethyl) glycoluril and the like. Among these N- (alkoxymethyl) glycoluril compounds, N, N, N ', N'-tetra (methoxymethyl) glycoluril is preferable.

Examples of N- (alkoxymethyl) melamine compounds include N, N, N ', N', N ", N" -hexa (methoxymethyl) melamine, N, N, N ', N', N ", N "-hexa (ethoxymethyl) melamine, N, N, N ', N', N", N "-hexa (n-propoxymethyl) melamine, N, N, N ', N', N", N "-hexa (i-propoxymethyl) melamine, N, N, N ', N', N", N "-hexa (n-butoxymethyl) melamine, N, N, N ', N', N ", N" -hexa (t-butoxymethyl) melamine and the like can be given. Among these N- (alkoxymethyl) melamine compounds, N, N, N ', N', N ", N" -hexa (methoxymethyl) melamine is preferable. As a commercial item, NIKALAC N-2702, MW-30M (above, Sanwa Chemical), etc. are mentioned, for example.

[J] As the usage-amount of the heat resistance improving agent, it is 50 mass parts or less with respect to 100 mass parts of [A] epoxy compounds, More preferably, it is 30 mass parts or less. When the compounding quantity of a [J] heat resistance improving agent exceeds 50 mass parts, a sensitivity may fall and a pattern shape may deteriorate.

<Preparation method of a coloring composition>

The coloring composition of this invention is a [A] epoxy compound, a [B] coloring agent, a [C] compound, a [D] amine compound, a [E] polymerizable compound as a suitable component, a [F] radiation sensitive polymerization initiator, and other It is prepared by mixing arbitrary components uniformly. This coloring composition is preferably dissolved in a suitable solvent and used in solution.

As a solvent used for preparation of the said coloring composition, an [A] epoxy compound, a [B] coloring agent, a [C] compound, a [D] amine compound, a [E] polymerizable compound, a [F] radiation sensitive polymerization initiator, and a necessity According to the present invention, those which dissolve other arbitrary components uniformly and do not react with each component are used. As such a solvent, the same thing as what was illustrated as a solvent which can be used for synthesize | combining the above-mentioned [A] epoxy compound is mentioned.

Among these solvents, for example, from the viewpoints of solubility of each component, reactivity with each component, ease of coating film formation, and the like, 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;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-meth (Poly) alkylene glycol monoalkyl ether acetates such as oxybutyl acetate;

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

Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexan-2-one Ketones such as these;

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

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

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, Ethyl oxyacetic acid, methyl 3-methoxy propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetate Other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate and ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, from the viewpoint of solubility, pigment dispersibility, coating property, etc. 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol Diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, Preferred are n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate. The solvent may be used alone or in combination of two or more.

In addition, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, benzoic acid together with the solvent You may use together high boiling point solvents, such as ethyl, diethyl oxalate, diethyl maleate, (gamma) -butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate. The said high boiling point solvent is single or two types. The above can be used.

Although it does not limit as content of a solvent, From the viewpoint of applicability | paintability, stability, etc. of the coloring composition obtained, the quantity by which the total concentration of each component except the solvent of the said coloring composition becomes 5 mass%-50 mass% is preferable, and 10 mass The amount which becomes% -40 mass% is more preferable.

When preparing the said coloring composition as a solution state, solid content concentration (components other than the solvent which occupies in a composition solution) is arbitrary density | concentration (for example, 5 mass%-50 mass%) according to a use purpose, the value of a desired film thickness, etc. ) Can be set. Although more preferable solid content concentration changes with the formation method of the coating film on a board | substrate, it mentions later. The composition solution thus prepared can be used for use after being filtered using a Millipore filter having a pore size of about 0.5 µm.

<Manufacturing method of color filter>

The coloring pattern and color filter formed from the said coloring composition are also contained suitably in this invention. The manufacturing method of the said color filter,

(1) Process of apply | coating the said coloring composition and forming a coating film on a board | substrate,

(2) forming a colored pattern on the coating film, and

(3) It has the process of baking the said coloring pattern at 200 degrees C or less.

Hereinafter, each process is explained in full detail.

[Step (1)]

This process is a process of forming the coating film of the said coloring composition on a board | substrate. On the surface of a board | substrate, a light shielding layer (black matrix) is formed so that the part which forms a pixel may be divided as needed. Next, after apply | coating the said coloring composition containing a red coloring agent, for example, on this board | substrate, prebaking is performed and the solvent is evaporated and a coating film is formed. As another method of forming a coloring pattern on a substrate, a method of obtaining pixels of each color by an inkjet method disclosed in JP-A-7-318723, JP-A-2000-310706 and the like can be adopted. . This method first forms a partition which also serves as a light shielding function on the surface of the substrate. Subsequently, after discharging the said coloring composition containing a red coloring agent by the inkjet apparatus in the formed partition, for example, prebaking is performed and the solvent is evaporated. Next, this coating film is exposed as needed to form a red pixel pattern. In addition, the partition wall has a film thickness thicker than that of the black matrix because it performs not only a light shielding function but also a function for preventing the colored compositions of each color discharged into the compartment from mixing.

As a material of a board | substrate, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example. In addition, these substrates may be subjected to a suitable pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition, or the like as desired.

As a method of apply | coating a coloring composition to a board | substrate, a spray method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, etc. are mentioned. Among these, the spin coating method and the slit die coating method are preferable.

Prebaking is normally performed combining pressure reduction drying and heat drying. As vacuum drying, it carries out until it reaches 50 Pa-200 Pa normally. Moreover, as conditions of heat drying, it is about 1 to 10 minutes at 70 degreeC-110 degreeC normally.

As film thickness after drying, it is 0.6 micrometer-8.0 micrometers normally, Preferably they are 1.2 micrometers-5.0 micrometers.

[Step (2)]

In this process, it is a process of forming a coloring pattern in the said coating film. A pixel array in which red pixel patterns are arranged in a predetermined array by exposing through a photomask to a coating film formed in step (1), developing using an alkaline developer, and dissolving and removing unexposed portions of the coating film. Is formed to form a colored pattern.

Subsequently, steps (1) and (2) are repeated using each colored composition of green or blue to form a green pixel array and a blue pixel array sequentially on the same substrate. Accordingly, a pixel array of three primary colors of red, green, and blue is disposed on the substrate. However, in this invention, the order and number of colors which form the pixel of each color are not limited to said thing.

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 photolithography method, but using the coloring composition containing a black colorant, the pixel It can be formed in the same manner as in the case of forming.

Examples of the light source for radiation include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, and argon ion lasers, YAG lasers, XeCl excimer lasers, and nitrogen. Laser light sources, such as a laser, etc. are mentioned. Radiation in the range of 190 nm-450 nm is preferable. As an exposure amount of radiation, 10J / m <2> -10,000J / m <2> is preferable.

Examples of the alkaline developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydrooxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3 .0] -5-nonene is preferred.

A suitable amount of water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. can be added to alkaline developing solution, for example. In addition, after alkali image development, water washing is normally carried out. 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 image development conditions, 5 second-300 second are preferable at normal temperature.

[Step (3)]

This process is a process of baking the said coloring pattern at 200 degrees C or less. After forming a coloring pattern in a process (2), baking (postbaking) is performed and hardening a coloring pattern and manufacturing a color filter. As heating conditions, it is 200 degrees C or less. As heating time, they are 10 minutes-60 minutes. In the present invention, even if the postbaking temperature is low, good coloring patterns such as solvent resistance can be obtained. Specifically, even if a postbaking temperature is 200 degrees C or less, and also 180 degrees C or less, the color filter which has sufficient solvent resistance etc. is obtained. As film thickness of a pixel, it is 0.5 micrometer-5.0 micrometers normally, Preferably they are 1.0 micrometer-3.0 micrometers.

<Color display element>

This invention also suitably includes the color display element provided with the said color filter. The said color display element 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 facing through the liquid crystal layer. Can be. In addition, a substrate in which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped tin) electrode is formed, face each other via a liquid crystal layer. You can also take The latter structure has the advantage that the aperture ratio can be significantly improved, and a bright and high definition liquid crystal display element is obtained.

(Example)

Hereinafter, although this invention is explained based on an Example, this invention is not limitedly interpreted by this Example.

<Synthesis of [A] epoxy compound>

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methylethyl ether were placed. Subsequently, 12 parts by mass of methacrylic acid as the compound (a1), 28 parts by mass of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl as the compound (a2) and 40 parts by mass of glycidyl methacrylate 20 parts by mass of styrene as a compound and (a3) was added, and the temperature of the solution was raised to 70 ° C. while the nitrogen was substituted and the stirring was continued gently. The solution containing the [A] copolymer (A-3) was obtained. Solid content concentration of the obtained polymer solution was 31.3%, and Mw of the copolymer (A-3) was 12,000.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methylethyl ether were placed. Subsequently, 18 parts by mass of methacrylic acid as the compound (a1), 23 parts by mass of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl as the compound (a2), 20 parts by mass of glycidyl methacrylate Part, 14 parts by mass of 2-methylglycidyl methacrylate, and 10 parts by mass of styrene as a compound (a3) and 15 parts by mass of methyl methacrylate, were put under nitrogen, followed by gentle stirring, and the temperature of the solution was continued. The solution containing the [A] copolymer (A-4) as an [A] epoxy compound was obtained by raising it to 70 degreeC and preserving and polymerizing this temperature for 5 hours. Solid content concentration of the obtained polymer solution was 31.5%, and Mw of the copolymer (A-4) was 10,100.

Synthesis Example 3

5 mass parts of 2,2'- azobis (isobutyronitrile) and 220 mass parts of 3-methoxybutyl acetates were put into the flask provided with a cooling tube and a stirrer. Subsequently, 18 parts by mass of methacrylic acid as the compound (a1), 36 parts by mass of methacrylic acid-3,4-epoxycyclohexyl methyl as the compound (a2), and 10 parts by mass of styrene as the compound (a3) and methacrylic acid 36 parts by mass of benzyl was added, while stirring was continued gently, the temperature of the solution was raised to 80 ° C, and the temperature was maintained for 5 hours to polymerize, thereby obtaining [A] copolymer (A-5) as the [A] epoxy compound. The solution containing was obtained. Solid content concentration of the obtained polymer solution was 30.9%, and Mw of the copolymer (A-5) was 9,800.

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobis (isobutyronitrile) and 220 parts by mass of propylene glycol monomethyl ether acetate were placed. Subsequently, 80 mass parts of benzyl methacrylate and 20 mass parts of methacrylic acid are put, and the temperature of a solution is raised to 80 degreeC, continuing stirring, and this temperature is preserve | saved and maintained for 5 hours, and a copolymer (CA A solution containing -1) was obtained. Solid content concentration of the obtained polymer solution was 31.0%, and Mw of the copolymer (CA-1) was 10,000.

<Preparation of a coloring composition>

The detail of each component used for preparation of each coloring composition is shown below.

[A] Epoxy Compound

A-1: 3, 4- epoxycyclohexyl methyl-3 ', 4'- epoxy cyclohexane carboxylate

A-2: phenol novolak-type epoxy resin (Japan epoxy resin company, Epicoat 152)

[B] colorants

B-1: C.I. Solvent Red 45

B-2: C.I. Solvent Yellow 98

B-3: C.I. Solvent Blue 67

B-4: C.I. Solvent Yellow 82

B-5: C.I. Solvent Blue 35

B-6: C.I. Solvent Blue 59

B-7: Valifast yellow 1101

B-8: C.I. Acid Black 24

[C] compound

C-1: 5-nitroisophthalic acid represented by a following formula

C-2: 5-hydroxyisophthalic acid represented by the following formula

C-3: 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane represented by the following formula

[D] amine compound

D-1: 2-phenyl-4-methyl-5-hydroxymethylimidazole

D-2: 2-methylimidazole

D-3: ethyl-4-methylimidazole

D-4: 2-methylbenzoimidazole

D-5: triethylamine

Clathrate compound

Z-1 to Z-10 as a clathrate compound shown below is a compound in which the [D] amine compound was clad in the said [C] compound as a host compound, respectively.

Z-1: C-1 (0.67 parts by mass) and D-1 (0.33 parts by mass) (2: 1)

Z-2: C-2 (0.67 parts by mass) and D-1 (0.33 parts by mass) (2: 1)

Z-3: C-3 (0.67 parts by mass) and D-1 (0.33 parts by mass) (2: 1)

Z-4: C-1 (0.67 parts by mass) and D-2 (0.33 parts by mass) (2: 1)

Z-5: C-2 (0.67 parts by mass) and D-2 (0.33 parts by mass) (2: 1)

Z-6: C-3 (0.67 parts by mass) and D-2 (0.33 parts by mass) (2: 1)

Z-7: C-1 (0.67 parts by mass) and D-3 (0.33 parts by mass) (2: 1)

Z-8: C-2 (0.67 parts by mass) and D-3 (0.33 parts by mass) (2: 1)

Z-9: C-3 (0.67 parts by mass) and D-3 (0.33 parts by mass) (2: 1)

Z-10: C-3 (0.50 parts by mass) and D-4 (0.50 parts by mass) (1: 1)

[E] polymerizable compound

E-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD® DPHA, Nippon Kayaku Co., Ltd.)

E-2: Mixture of polyfunctional acrylate compounds (KAYARAD® DPHA-40H, Nippon Kayaku Co., Ltd.)

E-3: 1,9-nonanediol diacrylate

E-4: pentaerythritol tetraacrylate

E-5: trimethylolpropane triacrylate

E-6: ω-carboxy polycaprolactone monoacrylate (Aronix M-5300, Toagose Co., Ltd.)

E-7: succinic acid modified pentaerythritol triacrylate (aronix TO-756, Toagose Co., Ltd.)

E-8: ethylene oxide modified dipentaerythritol hexaacrylate

[F] radiation sensitive polymerization initiator

F-1: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyl oxime)] (irgacure OXE01, Chiba Specialty Chemicals Co., Ltd.)

F-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (irgacure OXE02, Chiba? ? Chemicals Kabushi Kaisha)

F-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (irgacure 907, Chiba-Specialty Chemicals Co., Ltd.)

F-4: 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (irgacure 379, Chiba? Specialty chemicals) Kabushi Kaisha)

[G] Adhesion Aids

G-1: γ-glycidoxypropyltrimethoxysilane

[H] surfactant

H-1: Fluorine-type surfactant (FTX-218, Neos Co., Ltd.)

H-2: Silicone Surfactant (TORAY SILICON SH21PA, Torre Dow Corning Silicone Co., Ltd.)

[I] preservative stabilizers

I-1: 4-methoxyphenol

menstruum

S-1: Propylene Glycol Monomethyl Ether Acetate

S-2: cyclohexanone

S-3: ethyl lactate

[Examples 1-15 and Comparative Examples 1-4]

The kind shown in Table 1, [A] component of a compounding quantity, [B] coloring agent, [C] clathrate compound, [E] polymerizable compound, [F] radiation sensitive polymerization initiator, [G] adhesion adjuvant, [H] interface The coloring composition was prepared by mixing an active agent, a [I] storage stabilizer, and a solvent, adding a solvent so that solid content concentration might be 30 mass%, and then filtering by the Millipore filter of 0.5 micrometer of pore diameters. In addition, "-" in a column shows that the corresponding component was not used. In addition, it shows in Table 1 also about the measurement result of the viscosity (mPa? S) in 25 degreeC of each radiation sensitive resin composition.

<Evaluation>

The following evaluation was performed about the prepared coloring composition. A result is combined with Table 1 and shown.

[Storage Stability (%)]

The obtained coloring composition was left to stand in 40 degreeC oven for 1 week, the viscosity before and after heating was measured, the viscosity change rate (%) was calculated | required, and it was set as storage stability (%). The storage stability was judged to be good when the viscosity change rate was 5% or less, and the storage stability was determined to be poor when it exceeded 5%. In addition, the viscosity was measured at 25 degreeC using the E-type viscosity meter (VISCONIC® ELD.R, Toki Sangyo Co., Ltd.).

<Formation of a Colored Pattern>

A soda glass substrate SiO ₂ film is formed to prevent the elution of sodium ions on the surface, each of the coloring composition, was applied using a spin coater. Subsequently, prebaking was performed for 2 minutes on the 90 degreeC hotplate, and the film thickness after prebaking formed the 2.5 micrometer coating film. After cooling these board | substrates at room temperature, 100 (J / m <2>) and 300 (J) radiation which contains each wavelength of 365 nm, 405 nm, and 436 nm in a coating film via a photomask using a high pressure mercury lamp. / M 2), 500 (J / m 2), 700 (J / m 2), and 1,000 (J / m 2) of exposure doses. Subsequently, the developer was showered by discharging a developing solution (0.04 mass% potassium hydroxide aqueous solution at 23 ° C.) at a developing pressure of 1 (kgf / cm 2) (nozzle diameter of 1 mm) to the substrates, thereby coloring 200 × 200 μm on the substrate. The pattern was prepared. Furthermore, postbaking was performed at 180 degreeC for 30 minutes.

<Evaluation>

The following evaluation was performed about the formed coloring pattern. A result is combined with Table 1 and shown.

[Phenomena]

In formation of each said coloring pattern, image development tolerance (%) was evaluated from the film thickness ratio before and behind image development computed from the following formula.

Development resistance (%) = (film thickness after development / film thickness before development) x 100

When developing resistance is 95% or more, "A" (good judgment), less than 95%, or when a defect is recognized in part of the coloring pattern "B" (judged to be slightly poor), the pattern is peeled off from the substrate We assumed case to lose "C" (we judged to be defective).

[Heat resistance]

A colored pattern was formed in the same manner as the formation of the colored pattern except that the light was exposed at an exposure amount of 1,000 (J / m 2). Furthermore, it heated further at 180 degreeC for 30 minutes. And color change (DELTA) Eab ^* before and behind further heating was calculated | required. When ΔEab ^* was less than 3, "A" (good judgment), the case of 3 or more and less than 5 was set to "B" (a slight good judgment), and the case of 5 or more "C" (good judgment).

[Content selling]

It operated similarly to the said heat resistance evaluation, and formed the coloring pattern. This board | substrate was immersed for 30 minutes in 60 degreeC N-methylpyrrolidone. If the colored pattern is preserved after dipping and N-methylpyrrolidone after dipping is not colored at all, &quot; A &quot; The case where methylpyrrolidone is slightly colored is "B" (judged to be slightly good), the color pattern peeled off from the substrate after immersion is observed, and the case where N-methylpyrrolidone after immersion is colored is "C" (defective). I judged that).

[Voltage maintenance rate (%)]

A SiO ₂ film is formed on the surface to prevent elution of sodium ions, and the coating composition is spin coated on a soda glass substrate on which an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape. It prebaked for 10 minutes in the clean oven, and the coating film with a film thickness of 2.0 micrometers was formed. Subsequently, it exposed to the coating film by the exposure amount of 500 J / m <2> without interposing a photomask. Then, this board | substrate is immersed in the developing solution which consists of a 0.04 mass% potassium hydroxide aqueous solution at 23 degreeC for 1 minute, and after developing, it is wash | cleaned with ultrapure water, air-dried, and post-baking for 60 minutes at 180 degreeC further, hardening a coating film To form a permanent cured film. Subsequently, after bonding the board | substrate which formed this colored pattern and the board | substrate which only deposited the ITO electrode to a predetermined shape with the sealing compound which mixed 0.8 mm glass beads, the liquid crystal cell made by Merck (MLC6608) is inject | poured, and the liquid crystal cell is Made. Subsequently, the liquid crystal cell was put into the thermostat of 60 degreeC, and the voltage holding ratio of the liquid crystal cell was measured by the liquid crystal voltage holding ratio measurement system (VHR-1A type, Toyo Technica). The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. The voltage holding ratio is a value of (voltage applied at the liquid crystal cell potential difference / 0 millisecond after 16.7 milliseconds). When the voltage holding ratio of the liquid crystal cell is less than 90%, it means that the liquid crystal cell does not maintain the applied voltage at a predetermined level for a time of 16.7 milliseconds, and does not orient the liquid crystal sufficiently, and the term &quot; burn in &quot; High risk of causing.

<Production of a color filter>

The color filter was produced using the coloring composition (Example 3 red material, Example 4 green material, Example 5 blue material) of Examples 3-5. First, the coloring composition of Example 3 was apply | coated to the glass substrate in which the black matrix pattern was formed with the slit die coater, and it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film. Then, ghi line (wavelength ratio of 436 nm, 405 nm, 365 nm intensity = 2.7: 2.5: 4.8) was converted into i-line using an exposure machine Canon 노광 PLA501F (Canon Corporation) through a predetermined pattern mask. Irradiated at an exposure dose of 1,000 J / m 2, developed using 0.05% potassium hydroxide aqueous solution, rinsed with ultrapure water for 60 seconds, and further heated at 180 ° C. for 30 minutes in an oven to give a film thickness of 2.0 μm. A stripe pattern (pattern width 100 µm) was formed.

Then, it operated similarly and formed the green stripe pattern using the coloring composition of Example 4. Moreover, the blue stripe pattern was formed using the coloring composition of Example 5, and the red, green, and blue three-color stripe color filter (stripe width 100 micrometers) was formed. The red, green, and blue colored patterns formed under the conditions of the above-described post-baking temperature of 180 ° C. for 30 minutes have three-color stripes without problems such as defects in the pattern due to insufficient curing and peeling off from the substrate. A shape color filter could be formed. Furthermore, after apply | coating the composition for protective film formation (JNPC-48GLJJSR) on the obtained stripe-shaped color filter with a slit die coater, it prebakes at 90 degreeC for 5 minutes on a hotplate, and forms a coating film further, It heat-processed at 230 degreeC for 60 minute (s) in oven, and formed the protective film whose film thickness from the upper surface of a color filter was 2.0 micrometers.

[Measuring Flatness]

About the board | substrate which has a protective film on said color filter, the unevenness | corrugation (flatness) of the surface of a protective film was measured by the contact type film thickness measuring apparatus (alpha) -step (Tenco Japan Co., Ltd.) (measurement length 2,000 micrometers, measurement range 2,000) 탆 square, measured score n = 5). That is, the measurement direction is set as two directions of the stripe line short axis direction of red, green, and blue directions, and the stripe line major axis direction of the same color of red, red, green, green, and blue, and measurement at n = 5 for each direction. (N number of total is 10). Ten average values of the height difference (nm) between the highest part and the lowest part for every measurement were calculated | required. The average value at this time was 220 nm. Even after formation of the protective film, the coloring pattern was not contracted or expanded, and there was no irregularities on the surface of the protective film, and favorable flatness was shown.

The result of Table 1 showed that the coloring composition of this invention has favorable storage stability. Moreover, although the coloring pattern formed from the said coloring composition was formed by low temperature baking of 200 degrees C or less, it turned out that it is excellent in image development resistance, heat resistance, solvent resistance, and voltage retention. Moreover, it turned out that the color filter provided with the said coloring pattern is excellent in flatness.

According to the coloring composition of this invention, while containing the dye as a coloring agent, it is compatible with storage stability and low temperature baking, and the coloring pattern and color filter which are excellent in image development resistance, heat resistance, solvent resistance, voltage retention, etc. are obtained. Therefore, the said coloring composition is suitable for manufacture of various color filters, such as the color filter for color 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 flexible displays, such as an electronic paper. Can be used.

Claims (15)

[A] a compound having an epoxy group,
[B] a colorant,
[C] a compound having a hydroxyl group or a carboxyl group, and
[D] contains an amine compound,
The coloring composition whose viscosity in 25 degreeC is 1.0 mPa * s or more and 50 mPa * s or less. The method of claim 1,
The coloring composition in which an [D] amine compound can be included in a [C] compound. The method of claim 1,
[C] The compound is at least one compound selected from the group consisting of compounds represented by the following formulas (1) and (2), respectively, and the [D] amine compound is an imidazole compound or a benzimidazole compound Composition:

(In Formula (1), X is a single bond, a methylene group, or a C2-C6 alkylene group; R <^1> -R <^8> respectively independently represents a hydrogen atom, a C1-C12 alkyl group, a halogen atom, and C1-C? It is a phenyl group which may have a 12 alkoxy group or a substituent;
In formula (2), R <^9> is a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, or a hydroxyl group.). The method of claim 3,
The coloring composition whose compound represented by said Formula (1) is a compound represented by following formula (1-1):

(In formula (1-1), X and R <^1> -R <^8> have the same meaning as said Formula (1).). 5. The method according to any one of claims 1 to 4,
The coloring composition in which at least one part of [D] amine compound is included in [C] compound. 5. The method according to any one of claims 1 to 4,
[A] The coloring composition wherein the epoxy compound is a polymer. The method of claim 6,
The coloring composition in which the said polymer further has a carboxyl group. 5. The method according to any one of claims 1 to 4,
(E) The coloring composition further containing a polymeric compound which has an ethylenically unsaturated bond. 5. The method according to any one of claims 1 to 4,
[F] A coloring composition further comprising a radiation sensitive polymerization initiator. 5. The method according to any one of claims 1 to 4,
A coloring composition in which the clathrate compound in which the [D] amine compound is embedded in the [C] compound is prepared by mixing the [A] epoxy compound and the [B] colorant, and the viscosity at 25 ° C. is 1.0 mPa · s or more and 50 mPa · s or less. . [C] The clathrate compound in which the [D] amine compound is contained in the compound which has a hydroxyl group or a carboxyl group is mixed with the compound which has [A] epoxy group, and [B] coloring agent, and the viscosity in 25 degreeC is 1.0 mPa * s or more and 50 mPa The manufacturing method of the coloring composition which has a process of preparing to? s or less. The coloring pattern formed from the coloring composition of any one of Claims 1-4. The color filter provided with the coloring pattern of Claim 12. The color display element provided with the color filter of Claim 13. (1) Process of apply | coating the coloring composition of any one of Claims 1-4, and forming a coating film on a board | substrate,
(2) forming a colored pattern on the coating film, and
(3) The manufacturing method of the color filter which has a process of baking the said coloring pattern at 200 degrees C or less.