KR101336146B1 - Colored composition, colored pattern, color filter, color display device, and process for producing the color filter - Google Patents

Abstract

(Problem) The present invention relates to a color composition having a color composition that is excellent in developing stability, heat resistance, solvent resistance, voltage holding ratio, and the like, a color display element and a color filter having excellent storage stability and low temperature baking. It is to provide a manufacturing method.
(Solution means) [A] (A1) Copolymer having a carboxyl group-containing structural unit and (A2) Epoxy group-containing structural unit, [B] Polymerizable compound having ethylenically unsaturated bond, [C] Radiation-sensitive polymerization initiator, [D] a coloring agent and [E] the compound represented by following formula (1), the compound represented by following formula (2), a tertiary amine compound, an amine salt, a phosphonium salt, an amidine salt, an amide compound, a thiol compound, and a block isocyanate The coloring composition containing at least 1 sort (s) of hardening | curing agent chosen from the group which consists of a compound and an imidazole ring containing compound.

Description

Coloring composition, color pattern, color filter, color display element and method for producing color filter {COLORED COMPOSITION, COLORED PATTERN, COLOR FILTER, COLOR DISPLAY DEVICE, AND PROCESS FOR PRODUCING THE COLOR FILTER}

This invention relates to 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 and drying a pigment dispersion type coloring composition on a board | substrate, it irradiates (exposures) and develops the pixel of each color through this mask film through a mask pattern. The method of obtaining is known (refer patent document 1 and 2).

Moreover, in order to implement | achieve high contrast of a 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 3-5). In the coloring composition containing a dye, the hardening system which combined the polyfunctional acrylate, the alkoxy methyl melamine resin, etc., and a polymerization initiator 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 the low temperature of the baking process is needed (refer patent document 6).

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 obtained color filter is not satisfactory in developing resistance, voltage holding ratio and the like. Therefore, the addition of the amine compound used as a curing agent of the epoxy-based material can be considered a method of advancing the crosslinking reaction even at a low temperature.However, the addition of a general amine compound may cause a reaction over time with an epoxy group present in the composition. This may lower the storage stability.

In such a situation, development of a coloring composition which is compatible with storage stability and low temperature firing, and a coloring pattern and color filter excellent in development resistance, heat resistance, solvent resistance, voltage holding ratio and the like 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. 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, and the coloring pattern, color filter, color filter which are excellent in image development resistance, heat resistance, solvent resistance, voltage retention, etc. It is to provide a color display device and a manufacturing method of a color filter having a.

According to an aspect of the present invention,

[A] A copolymer having a (A1) carboxyl group-containing structural unit and (A2) epoxy group-containing structural unit (hereinafter, may be referred to as "[A] copolymer"),

[B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter may be referred to as "[B] polymerizable compound"),

[C] radiation sensitive polymerization initiator (hereinafter may be referred to as "[C] polymerization initiator"),

[D] a colorant, and

[E] Compound represented by the following formula (1), compound represented by the following formula (2), tertiary amine compound, amine salt, phosphonium salt, amidine salt, amide compound, thiol compound, blocked isocyanate compound and imidazole ring-containing At least 1 type of hardening | curing agent chosen from the group which consists of a compound (Hereinafter, it may be called "[E] hardening | curing agent.))

It is a coloring composition containing.

(In formula (1), R <^1> -R <^6> is respectively independently a hydrogen atom, an electron withdrawing group, or an amino group; However, R <^1> -R <^6> At least one is an electron withdrawing group, and R ¹ to R ⁶ At least one of is an amino group; Moreover, all or one part of hydrogen atoms may be substituted by the C1-C6 alkyl group of the said amino group;

In the formula (2), R ⁷ to R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group or an amino group; Provided that R ⁷ to R ¹⁶ At least one of is an amino group; Moreover, all or one part of hydrogen atoms may be substituted by the C1-C6 alkyl group of the said amino group; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms; Provided that all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group).

The coloring composition contains an [E] curing agent selected from the specific compounds while containing the [D] coloring agent as a coloring agent, thereby acting as an effective curing catalyst for the epoxy group of the [A] copolymer and the like, and conserving the result. Stability and low temperature firing are compatible. Moreover, even if it is a low exposure amount, the coloring pattern etc. which were excellent by image development tolerance, heat resistance, solvent resistance, and voltage retention are obtained by containing a [B] polymeric compound and a [C] polymerization initiator.

It is preferable that [E] hardening | curing agent is at least 1 sort (s) chosen from the group which consists of a compound represented by said Formula (1) and Formula (2). By selecting the said specific compound which has an amino group and an electron deficient group as a [E] hardening | curing agent, the storage stability and low temperature baking of the said coloring composition can be made compatible at a higher level, and the voltage retention rates, such as a coloring pattern obtained further, are further improved. You can.

It is preferable that the said coloring composition further contains the copolymer (Hereinafter, it may be called "[F] copolymer") which has a [F] radical reactive functional group.

When the said coloring composition contains a [F] copolymer, the coloring composition by which the agent characteristic, such as image development tolerance and storage stability, was balanced to a higher level is obtained.

The coloring pattern formed from the said coloring composition which exhibits such an effect, and the color filter provided with this coloring pattern are also contained suitably for this invention.

The manufacturing method of the color filter of this invention,

(1) forming a coating film of the coloring composition on a substrate;

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

(3) It has the process of baking the coating film in which the said coloring pattern was formed at 200 degrees C or less.

By the manufacturing method of the color filter of this invention using the said coloring composition, the color filter with favorable heat resistance, chemical-resistance, voltage holding ratio, etc. can be formed. In addition, as mentioned above, since the said coloring composition contains a specific component, low temperature baking can be implement | achieved and baking at the temperature of 200 degrees C or less in the said process (3) becomes possible. Therefore, the color filter manufactured in this way is suitable for the flexible display in which low temperature baking is desired.

The color display element of this invention is equipped with the color filter formed from the said coloring composition. In addition, it can be used suitably for manufacture of various color filters, such as the color filter for color separation of a solid-state image sensor, and the color filter for organic electroluminescent display elements.

In addition, "baking" as used in this specification means heating until the intensity | strength required for a coloring pattern and a color filter is obtained. In addition, "radiation" irradiated at the time of exposure is a concept containing visible light, an ultraviolet-ray, far ultraviolet rays, X-rays, a charged particle beam, etc.

According to the coloring composition of this invention, while containing 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 tolerance, 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.

(Mode for carrying out the invention)

<Coloring composition>

The coloring composition of this invention contains a [A] copolymer, a [B] polymeric compound, a [C] polymerization initiator, a [D] coloring agent, and a [E] hardening | curing agent. Moreover, you may contain a [F] copolymer as a suitable component. Moreover, you may contain other arbitrary components, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.

<[A] Copolymer>

The copolymer (A) is a copolymer having a (A1) carboxyl group-containing structural unit and (A2) epoxy group-containing structural unit (hereinafter, may be referred to as "[A] copolymer").

[A] copolymer can be manufactured by copolymerizing the (A1) compound which gives a carboxyl group containing structural unit and the (A2) compound which gives an epoxy group containing structural unit in presence of a polymerization initiator, for example. . Moreover, the hydroxyl group containing unsaturated compound (henceforth a "(A3) compound" may be called hereafter) which gives a hydroxyl group containing structural unit (A3) can be further added, and it can be set as a copolymer. In the production of the copolymer [A], together with the compound (A1), the compound (A2) and the compound (A3), the compound (A4) is derived from the compound (A1), (A2) and (A3). Unsaturated compound which gives structural units other than the structural unit to be added) can be further added, and it can be set as a copolymer.

[(A1) Compound]

Examples of the compound (A1) include unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, anhydride of unsaturated dicarboxylic acid, mono [(meth) acryloyloxyalkyl] ester of polyvalent carbonic acid, and a polymer having a carboxyl group and a hydroxyl group at both ends. Mono (meth) acrylate, an unsaturated polycyclic compound having a carboxyl group, and anhydrides thereof.

As unsaturated monocarboxylic acid, For example, acrylic acid, methacrylic acid, crotonic acid, etc .;

As unsaturated dicarboxylic acid, For example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .;

As anhydride of unsaturated dicarboxylic acid, For example, anhydride etc. of the compound illustrated as said dicarboxylic acid;

As mono [(meth) acryloyloxyalkyl] ester of polyhydric carboxylic acid, for example, succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Etc;

As mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group in both terminal, For example, (omega) -carboxy polycaprolactone mono (meth) acrylate;

Examples of the unsaturated polycyclic compound having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [ 2.2.1] hepto-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride, etc. Can be mentioned.

Of these, monocarboxylic acid and dicarboxylic acid anhydride are preferable, and acrylic acid, methacrylic acid and maleic anhydride are more preferable in terms of copolymerization reactivity, solubility in aqueous alkali solution and ease of obtaining. These (A1) compounds may be used independently or may be used in mixture of 2 or more type.

As a usage ratio of a compound (A1), 5-30 mass% is preferable based on the sum total of (A1) compound and (A2) compound (optional (A3) compound and (A4) compound as needed). And 10 mass%-25 mass% are more preferable. By setting the use ratio of the compound (A1) to 5% by mass to 30% by mass, the solubility in the aqueous alkali solution of the [A] copolymer is optimized, and a colored composition excellent in radioactivity sensitivity is obtained.

[(A2) Compound]

The compound (A2) is an epoxy group-containing unsaturated compound. As an epoxy group, an oxiranyl group (1, 2- epoxy structure) and an oxetanyl group (1, 3- epoxy structure) are mentioned.

Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-propyl acrylate. , α-n-butyl acrylate glycidyl, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl Acrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, methacrylic acid 3,4-epoxycyclohexylmethyl, and the like. Can be. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinyl benzyl glycidyl ether and methacrylic acid 3,4-epoxycyclohexylmethyl are preferable from the viewpoint of improvement of solvent resistance, such as copolymerization reactivity and a coloring pattern.

As an unsaturated compound which has an oxetanyl group, for example

3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyl Oxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (Acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl)- 2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2 -Acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-acryloyloxyethyl) -2-penta Fluoroethyl oxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2,2-difluorooxetane, 3- (2 -Acryloyloxyethyl) -2,2,4-trifluoro Oxetane, 3- (2-oxyethyl acrylate), acrylic acid esters such as oxetane -2,2,4,4- tetrafluoroethane;

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) (Methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2- (Methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (Methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) 3- (2-methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-methacryloyloxyethyl) (2-methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- ) -2,2-difluorooxetane, 3- (2- Methacrylic acid, such as kryloyloxyethyl) -2,2,4-trifluorooxetane and 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane Ester etc. are mentioned. These (A2) compounds may be used independently or may be used in mixture of 2 or more type.

As a use ratio of the (A2) compound, 5 mass%-60 mass% are preferable based on the sum total of (A1) compound and (A2) compound (optional (A3) compound and (A4) compound as needed). And 10 mass%-50 mass% are more preferable. By setting the use ratio of the compound (A2) to 5% by mass to 60% by mass, a coloring pattern or the like having excellent solvent resistance or the like can be formed.

[(A3) Compound]

As a (A3) compound, the (meth) acrylic acid ester which has a hydroxyl group, the phenolic hydroxyl group containing unsaturated compound represented by following formula (3), etc. are mentioned.

In said formula (3), R <^17> is a hydrogen atom or a C1-C4 alkyl group. R ¹⁸ to R ²² each independently represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Y is a single bond, -COO-, or -CONH-. p is an integer of 0-3. Provided that at least one of R ¹⁸ to R ²² is a hydroxyl group.

As (meth) acrylic acid ester which has the said hydroxyl group, For example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, polyethylene glycol (n = 2-10) mono (meth) acrylate, polypropylene glycol (n = 2-10) mono (meth) acrylate, 2,3-dihydroxypropyl (meth) Acrylate, 2-methacryloxyethyl glycoside, etc. are mentioned.

As a phenolic hydroxyl group containing unsaturated compound represented by said Formula (3), the compound etc. which are represented by following formula (3-1)-formula (3-5) are mentioned, for example by definition of Y and p.

In said formula (3-1), q is an integer of 1-3. R ¹⁷ to R ²² have the same meaning as in Formula (3).

In said formula (3-2), R <^17> -R <^22> is synonymous with said formula (3).

In said formula (3-3), r is an integer of 1-3. R ¹⁷ to R ²² have the same meaning as in Formula (3).

In said formula (3-4), R <^17> -R <^22> is synonymous with said formula (3).

In said formula (3-5), R <^17> -R <^22> is synonymous with said formula (3).

Among these (A3) compounds, 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, o-hydroxy styrene, p-hydroxy styrene and α-methyl-p-hydroxy styrene are preferable. These (A3) compounds may be used independently or may be used in mixture of 2 or more type.

As a usage ratio of a compound (A3), 1 mass%-30 mass% are preferable based on the sum total of (A1) compound, (A2) compound, and (A3) compound (optional (A4) compound as needed). And 5 mass%-25 mass% are more preferable. By setting the use ratio of the compound (A3) in the above range, a coloring pattern or the like having excellent solvent resistance or the like can be formed.

[(A4) Compound]

The compound (A4) is not particularly limited as long as it is an unsaturated compound other than the compound (A1), the compound (A2) and the compound (A3). As the (A4) compound, for example, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bi Cyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, tetrahydrofuran skeletons, furan skeletons, tetrahydropyran skeletons, pyran skeletons, unsaturated compounds comprising a skeleton represented by the following formula (4), and other unsaturated compounds Can be mentioned.

In said formula (4), R <^23> is a hydrogen atom or a methyl group. s is an integer of 1 or more.

As methacrylic acid linear alkylester, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, Isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, etc. are mentioned.

As methacrylic acid cyclic alkylester, for example, methacrylic acid cyclohexyl, methacrylic acid 2-methylcyclohexyl, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate, etc. are mentioned.

As acrylic acid linear alkyl ester, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, N-stearyl acrylic acid etc. are mentioned.

Examples of the acrylic acid cyclic alkyl esters include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] Decan-8-yloxyethyl acrylate, isobornyl acrylate, and the like.

As methacrylic acid aryl ester, methacrylate phenyl, benzyl methacrylate, etc. are mentioned, for example.

As acrylic acid aryl ester, phenyl acrylate, benzyl acrylate, etc. are mentioned, for example.

As unsaturated dicarboxylic acid diester, diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. are mentioned, for example.

Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene and 5-ethylbicyclo [2.2.1] hepto- 2-ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dimethoxybicyclo [2.2.1 ] Hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclo Hexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-di (t-butoxycarbonyl) Bicyclo [2.2.1] hepto-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1] hepto-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto- 2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2. 2.1] hepto-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hepto-2-ene, etc. are mentioned.

As a maleimide compound, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, for example , N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide Propionate, N- (9-acridinyl) maleimide, and the like.

As an unsaturated aromatic compound, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene, etc. are mentioned, for example.

Examples of the conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

As an unsaturated compound containing a tetrahydrofuran skeleton, it is tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxy tetrahydro, for example. Furan-2-one etc. are mentioned.

As an unsaturated compound containing a furan skeleton, 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-, for example 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-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethylester, 6- (2-furyl) -6-methyl-1-heptene-3- On etc. can be mentioned.

As an unsaturated compound containing tetrahydropyran skeleton, it is (tetrahydropyran-2-yl) methylmethacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -octo-1, for example. -En-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, etc. are mentioned.

Examples of the unsaturated compound containing a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran and 4- (1,5-dioxa- 6-oxo-7-octenyl) -6-methyl-2-pyran etc. are mentioned.

As other unsaturated compounds, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, etc. are mentioned, for example.

Among these (A4) compounds, methacrylic acid chain alkyl esters, methacrylic acid cyclic alkyl esters, maleimide compounds, tetrahydrofuran skeletons, furan skeletons, tetrahydropyran skeletons, pyran skeletons, and the skeletons represented by the formula (4) The unsaturated compound which has, an unsaturated aromatic compound, and acrylic acid cyclic alkylester is preferable. Among these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexyl maleimide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2-10) mono (meth) acrylate, 3- ( Meta) acryloyloxytetrahydrofuran-2-one is more preferable at the point of copolymerization reactivity and the solubility to aqueous alkali solution. These (A4) compounds may be used independently or may be used in mixture of 2 or more type.

As a usage ratio of a compound (A4), 10 mass%-70 mass% are preferable based on the sum total of (A1) compound, (A2) compound, and (A4) compound (and arbitrary (A3) compound), 20 Mass%-60 mass% are more preferable. By setting the use ratio of the compound (A4) to 10% by mass to 70% by mass, a coloring pattern and the like excellent in solvent resistance and the like can be formed.

<Synthesis method of [A] copolymer>

The copolymer (A) can be produced by copolymerizing the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound) in the presence of a polymerization initiator, for example.

Examples of the solvent used in the polymerization reaction for producing the copolymer (A) include alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, diethylene glycol dialkyl ether, and dipropylene glycol dialkyl ether. , Propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, ester and the like.

As alcohol, For example, benzyl alcohol;

As glycol ether, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether;

As ethylene glycol alkyl ether acetate, For example, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .;

As diethylene glycol monoalkyl ether, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc .;

As diethylene glycol dialkyl ether, For example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As dipropylene glycol dialkyl ether, For example, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ether, For example, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc .;

As propylene glycol monoalkyl ether acetate, For example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate etc .;

As propylene glycol monoalkyl ether propionate, For example, propylene glycol monomethyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, etc .;

As a ketone, For example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanone, methyl isoamyl ketone, etc .;

Examples of the ester include ethyl acetate, butyl acetate, 3-methoxybutyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, and hydroxy. Butyl acetate, methyl lactate, ethyl lactate, propyl lactic acid, butyl lactate, 2-ethoxypropionate ethyl, 2-ethoxypropionic acid propyl, 2-ethoxypropionate butyl, 2-butoxypropionate methyl, 2-butoxypropionate, 2-butoxypropionic acid propyl, 2-butoxypropionic acid butyl, 3-methoxypropionic acid methyl, 3-methoxypropionic acid ethyl, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl, 3-ethoxypropionic acid methyl, 3 Ethyl ethoxypropionate, propyl 3-ethoxypropionic acid, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, and the like.

Among these solvents, 3-methoxybutyl acetate, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether and propylene glycol alkyl ether acetate are preferable, and 3-methoxy acetate Butyl, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are more preferable.

As a polymerization initiator used for the polymerization reaction for manufacturing [A] copolymer, what is generally known as a radical polymerization initiator can be used. As a radical polymerization initiator, 2,2'- azobisisobutyronitrile (AIBN), 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2'- azobis-, for example Azo compounds such as (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, 1,1'-bis- (t-butylperoxy) cyclohexane, and hydrogen peroxide. When using a peroxide as a radical polymerization initiator, you may use a peroxide together with a reducing agent as a redox type initiator.

In the polymerization reaction for manufacturing the copolymer (A), in order to adjust the molecular weight, 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; Azetidine derivatives such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Terpinolene, alpha -methylstyrene dimer, and the like.

As a weight average molecular weight (Mw) of the copolymer (A), 1,000-30,000 are preferable and 5,000-20,000 are more preferable. By making Mw of a copolymer (A) into the said range, the sensitivity and developability of the said coloring composition can be improved. In addition, Mw and the number average molecular weight (Mn) of the polymer in this specification were measured by the gel permeation chromatography (GPC) by the following 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

Column temperature: 40 DEG C

Flow rate: 1.0mL / min

Sample concentration: 1.0 mass%

Sample injection volume: 100 uL

Detector: differential refractometer

Standard material: monodisperse polystyrene

&Lt; [B] Polymerizable compound >

Examples of the polymerizable compound [B] contained in the coloring composition include ω-carboxypolycaprolactone (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) acrylate, bisphenoxyethanol fluorenedi (Meth) acrylate, dimethylol tricyclodecanedi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2'-vinyloxyethoxy) ethyl ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (C) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, succinic acid modified pentaerythritol tri (meth) acrylate, etc. Urethane obtained by reacting a compound having an alkylene group and an alicyclic structure and having at least two isocyanate groups with a compound having at least one hydroxyl group in the molecule and having 3 to 5 (meth) acryloyloxy groups (meta ) Acrylate compound and the like.

As a commercially available product of the polymerizable compound [B], for example,

Aronix M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, M-7100, M- 8030, East M-8060, East M-8100, East M-8530, East M-8560, East M-9050, Aronix TO-756, East TO-1450, East TO-1382 (above, Toagosei Co., Ltd.) ), KAYARAD 'DPHA, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120, East MAX-3510 (above, Nippon Kayaku Co., Ltd.), Viscoat 295, East 300, East 360, east GPT, east 3PA, east 400 (above, Osaka Yukikagaku Co., Ltd.), urethane acrylate-based New Frontier® R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD 'DPHA -40H, UX-5000 (Nippon Kayaku Co., Ltd.), UN-9000H (Negami Kogyo Co., Ltd.), Aronix M-5300, East M-5600, East M-5700, East 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 KAYARAD 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 Kaya KU Kabushiki Kaisha), Art-Resin UN-9000PEP, East UN-9200A, East UN-7600, East UN-333, East UN-1003, East UN-1255, East UN-6060PTM, East UN- 6060P, East SH-500B (above, Negami Kogyo Co., Ltd.), Biscot 260, East 312, East 335HP (above, Osaka Yuki Kagaku Co., Ltd.), etc. are mentioned.

The polymerizable compound (B) may be used alone or in combination of two or more thereof. As a use ratio of the [B] polymeric compound in the said coloring composition, 10 mass parts-700 mass parts are preferable with respect to 100 mass parts of [A] copolymers, and 20 mass parts-600 mass parts are more preferable. By setting the use ratio of the polymerizable compound (B) in the above range, the colored composition can form a colored pattern having sufficient heat resistance, solvent resistance, and voltage holding ratio even at a low exposure amount.

<[C] polymerization initiator>

The polymerization initiator [C] contained in the coloring composition is a component that generates active species capable of initiating polymerization of the polymerizable compound [B] in response to radiation. As such a [C] polymerization initiator, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, etc. are mentioned. These compounds may be used independently or may be used in mixture of 2 or more type.

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 Hydropyranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1, 3-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) And the like.

Among them, 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole- 3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxoranyl) methoxy Benzoyl} -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.

Examples of the? -amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- 1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one .

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-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, α-amino ketone compounds are preferable, and 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 and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are more preferable Do.

As a biimidazole compound, it is a 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetrakis (4-ethoxycarbonylphenyl) -1,2' ratio, for example. Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5, 5'-tetra phenyl-1,2'-biimidazole etc. are mentioned. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole is preferred, and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2' -Biimidazole is more preferred.

As a usage ratio of the [C] polymerization initiator, 1 mass part-40 mass parts are preferable with respect to 100 mass parts of [A] copolymers, and 5 mass parts-30 mass parts are more preferable. By making the use ratio of the (C) polymerization initiator into 1 mass part-40 mass parts, even if it is a low exposure amount, the said coloring composition can form the coloring pattern and color filter which have high solvent resistance etc ..

<[D] colorant>

It will not specifically limit, if it has coloring property as [D] coloring agent contained in the said coloring composition, A color and a material can be suitably selected according to the use of a coloring pattern and a color filter. As the colorant, for example, any of pigments, dyes, and natural dyes can be used. However, pigments and dyes are preferable, and dyes are more preferable, since high color purity, brightness, contrast, and the like are required for the coloring patterns and color filters. .

As a 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 the 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, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 55, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 211;

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

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

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

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

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

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

C.I. Pigment Black 1, C.I. Pigment Black 7 and the like.

In addition, examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc sulfur, lead sulfate, yellow lead, zinc sulfur, bengal (red iron oxide (III)), cadmium red, ultramarine blue, and blue blue ( iron blue), chromium oxide green, cobalt green, enver, titanium black, synthetic iron black, carbon black, and the like.

As the dye, any known dye can be used as long as it is soluble in an organic solvent. 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.

Examples of the dye include oil-soluble dyes, acid dyes or derivatives thereof, direct dyes, and modern dyes.

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

C.I. Solvent Yellow 4 (hereinafter, the description of “CI Solvent Yellow” is omitted, only the number is described and other dyes are also described in the same manner), 14, 15, 23, 24, 38, 62, 63, 68, 82, 88, 94, 98, 99, 162, 179;

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

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

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

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

C.I. As an acid dye, for example

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

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

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

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

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

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

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

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

C.I. As a direct dye, for example

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138, 141;

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

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

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

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

C.I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like.

C.I. As a modern dye, for example

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

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

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

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

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

C.I. Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like.

As content of the [D] coloring agent, 1 mass part-400 mass parts are preferable with respect to 100 mass parts of [A] copolymers, and 5 mass parts-350 mass parts are more preferable. By making content of a coloring agent (D) into the said range, the alkali developability of a coloring composition, the heat resistance of a pixel, solvent resistance, a coloring pattern, and the high brightness and high contrast as a color filter can be achieved at a high level with good balance.

<[E] Curing Agent>

The hardening | curing agent [E] which the said coloring composition contains is a compound represented by said formula (1), the compound represented by said formula (2), a tertiary amine compound, an amine salt, a phosphonium salt, an amidine salt, an amide compound, a thiol compound , At least one selected from the group consisting of blocked isocyanate compounds and imidazole ring-containing compounds. When the said coloring composition contains the [E] hardening | curing agent selected from the said specific compound, storage stability and low temperature baking can be compatible. Hereinafter, each compound is explained in full detail.

[Compound represented by Formula (1) and Formula (2)]

It is preferable that it is at least 1 sort (s) chosen from the group which consists of a compound represented by said Formula (1) and Formula (2) as [E] hardening | curing agent. By selecting the said specific compound which has an amino group and an electron deficient group as a [E] hardening | curing agent, the storage stability and low temperature baking of the said coloring composition can be made compatible at a higher level, and the voltage retention rates, such as a coloring pattern obtained further, are further improved. You can.

In the above formula (1), R ¹ to R ⁶ are each independently a hydrogen atom, an electron-withdrawing group or an amino group. Provided that at least one of R ¹ to R ⁶ is an electron withdrawing group, and at least one of R ¹ to R ⁶ is an amino group, and all or part of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms. good.

In the formula (2), R ⁷ to R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group or an amino group. Provided that at least one of R ⁷ to R ¹⁶ is an amino group. In addition, all or part of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms. A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms. The methylene group and the alkylene group may be substituted with a cyano group, a halogen atom or a fluoroalkyl group in all or a part of hydrogen atoms.

As an electron withdrawing group which said R <^1> -R <^16> represents, for example, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an acyl group, an alkylsulfonyl group, an alkyloxysulfonyl group, and a dicyano vinyl group , Tricyano vinyl group, sulfonyl group and the like. Of these, a nitro group, an alkyloxysulfonyl group and a trifluoromethyl group are preferable. As group which A represents, the methylene group which may be substituted by the sulfonyl group and the fluoroalkyl group is preferable.

As a compound represented by said Formula (1) and Formula (2),

2,2-bis (4-aminophenyl) hexafluoropropane, 2,3-bis (4-aminophenyl) succinonitrile, 4,4'-diaminobenzophenone, 4,4'-diaminophenylbenzo 8,4,4'-diaminodiphenylsulfone, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2-bromobenzene, 1,4-diamino-2-iodobenzene , 1,4-diamino-2-nitrobenzene, 1,4-diamino-2-trifluoromethylbenzene, 2,5-diaminobenzonitrile, 2,5-diaminoacetophenone, 2,5- Diaminobenzoic acid, 2,2'-dichlorobenzidine, 2,2'-dibromobenzidine, 2,2'-diiodobenzidine, 2,2'-dinitrobenzidine, 2,2'-bis (trifluor Romethyl) benzidine, 3-aminobenzenesulfonic acid ethyl, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline are preferable, 4,4'-diaminodiphenylsulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (trifluoromethyl) benzidine, 3-aminobenzenesulphone More preferred are acid ethyl, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline.

The compound represented by said Formula (1) and Formula (2) can be used individually or in mixture of 2 or more types. As a content rate of the compound represented by said Formula (1) and Formula (2), 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of [A] copolymer, and 0.2 mass part-10 mass parts are more preferable. By making the content rate of the compound represented by said Formula (1) and Formula (2) into the said range, the storage stability of the said coloring composition and low temperature baking can be compatible to a higher level.

[Tertiary amine compound]

When a highly reactive general primary amine compound and secondary amine compound coexist with an epoxy compound, hardening reaction advances by nucleophilic attack of an amine to an epoxy group during storage of a composition solution, and there exists a possibility that the quality as a product may be impaired. However, when tertiary amine is used, the storage stability becomes good even if it coexists with an epoxy compound in a cognitive composition part because of relatively low reactivity.

As a tertiary amine compound, at least 1 sort (s) chosen from the group which consists of a compound represented by following formula (5) can be used.

In said formula (5), R <^24> -R <^26> is a C1-C20 alkyl group, a C6-C18 aryl group, or a C7-C30 aralkyl group each independently. However, R ²⁴ and R ²⁵ may be bonded to each other to form a ring structure with the nitrogen atom to which they are bonded. Some or all of the hydrogen atoms may be substituted for the alkyl group, the aryl group, and the aralkyl group.

As said C1-C20 alkyl group which said R <^24> -R <^26> represents, a linear or branched methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl group, lauryl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc. are mentioned.

As a C6-C18 aryl group which said R <^24> -R <^26> represents, a phenyl group, a naphthyl group, etc. are mentioned, for example.

As a C7-C30 aralkyl group which said R <^24> -R <^26> represents, a benzyl group, a phenethyl group, etc. are mentioned, for example.

As the tertiary amine compound, for example, trimethylamine, triethylamine, N, N-dimethyl benzylamine, triphenylamine, tributylamine, trioctylamine, tridodecylamine, dibutylbenzylamine, trinaphthylamine , N-ethyl-N-methylaniline, N, N-diethylaniline, N-phenyl-N-methylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-4-bromoaniline, N , N-dimethyl-4-methoxyaniline, N-phenylpiperidine, N- (4-methoxyphenyl) piperidine, N-phenyl-1,2,3,4-tetrahydroisoquinoline, 6- Benzyloxy-N-phenyl-7-methoxy-1,2,3,4-tetrahydroisoquinoline, N, N'-dimethylpiperazine, N, N-dimethylcyclohexylamine, 2-dimethylaminomethylphenol, 2,4,6-tris (dimethylaminomethyl) phenol etc. are mentioned.

Among these tertiary amine compounds, triethylamine, trioctylamine, 2-dimethylaminomethyl phenol, N, N-diethylaniline, and the like are preferable. The tertiary amine compounds may be used alone or in combination of two or more. As a content rate of the tertiary amine compound in the said coloring composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] copolymer, and 0.5 mass part-5 mass parts are more preferable. By making the content rate of a tertiary amine compound into the said specific range, the storage stability of the said coloring composition and low temperature baking can be compatible at a higher level.

[Amine salts and phosphonium salts]

As an amine salt and a phosphonium salt, at least 1 sort (s) chosen from the group which consists of a compound represented by following formula (6) can be used.

In said formula (6), A <^1> is a nitrogen atom or a phosphorus atom. R ²⁷ to R ³⁰ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. However, these groups may be substituted with some or all of the hydrogen atoms. Q ⁻ is a monovalent anion.

As a C1-C20 alkyl group which said R <^27> -R <^30> represents, a linear or branched methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl group, lauryl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc. are mentioned.

As a C6-C18 aryl group which said R <^27> -R <^30> represents, a phenyl group, a naphthyl group, etc. are mentioned, for example.

As a C7-C30 aralkyl group which said R <^27> -R <^30> represents, a benzyl group, a phenethyl group, etc. are mentioned, for example.

Examples of the monovalent anion represented by Q ⁻ include chloride ion, bromide ion, iodide ion, cyanide ion, nitrate ion, nitrite ion, hypochlorite ion, chlorite ion, chlorate ion, perchlorate ion, permanganate ion, Hydrogen carbonate ion, dihydrogen phosphate ion, hydrogen sulfide ion, thiocyanate ion, carbonic acid ion, sulfonic acid ion, phenoxide ion, tetrafluoroborate ion, tetraarylborate ion, hexafluoroantimonate ion and the like Can be.

When A ¹ is a nitrogen atom, that is, as an ammonium salt, for example, tetramethyl ammonium chloride, tetrabutyl ammonium chloride, dodecyldimethylbenzyl ammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetrachloride, etc. Decyl trimethylammonium, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzalkonium chloride, benzalkonium bromide, didecyldimethylammonium chloride, distearyl chloride Dimethyl ammonium is mentioned.

In the case where A ¹ is a phosphorus atom, that is, as a phosphonium salt, for example, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (p-tolyl) borate, tetraphenylphosphonium tetra (p-ethylphenyl) ) Borate, tetraphenylphosphonium tetra (p-methoxyphenyl) borate, tetraphenylphosphonium tetra (p-ethoxyphenyl) borate, tetraphenylphosphonium tetra (p-tert-butoxyphenyl) borate, Tetraphenylphosphonium tetra (m-tolyl) borate, tetraphenylphosphonium tetra (m-methoxyphenyl) borate, tri (p-tolyl) phenylphosphonium tetra (p-tolyl) borate, tetra (p- Tolyl) phosphonium tetra (p-tolyl) borate, tri (p-methoxyphenyl) phenyl phosphonium tetra (p-tolyl) borate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, Methyltriphenylphosphonium thiocyanate, p-tolyltri Nylphosphonium thiocyanate, benzyltriphenylphosphonium hexafluoroantimonate, p-chlorobenzyltriphenylphosphonium hexafluoroantimonate, p-methylbenzyltriphenylphosphonium hexafluoroantimonate, p -Methoxybenzyltriphenylphosphonium hexafluoroantimonate, α-methylbenzyltriphenylphosphonium hexafluoroantimonate, cinnamiltriphenylphosphonium hexafluoroantimonate, 2-hydroxy-5- Nitrobenzyltriphenylphosphonium hexafluoroantimonate, 1-naphthylmethyltriphenylphosphonium hexafluoroantimonate, 3-trimethylsilyl-4-trimethylsiloxybenzyltriphenylphosphonium hexafluoroantimonate , p-methoxybenzyltris (p-chlorophenyl) phosphonium hexafluoroantimonate, p-methoxybenzyltris (p-methylphenyl) phosphonium hexafluoroantimonate, cinnamiltris (p-chlorofe ) Phosphonium hexafluoroantimonate, p-methoxybenzyltriphenylphosphonium hexafluorophosphate, 1-pyrenylmethyl-triphenylphosphonium hexafluoroantimonate, 1-pyrenylmethyl- Butyl diphenyl phosphonium hexafluoro antimonate, 9-anthracenylmethyl- triphenyl phosphonium hexafluoro antimonate, tetrabutyl phosphonium decane salt, tri (tert- butyl) phosphonium tetraphenyl borate, di -tert- butylmethyl phosphonium tetraphenyl borate, p-tolyl triphenyl phosphonium tetra (p-tolyl) borate, tetraphenyl phosphonium tetrafluoro borate, etc. are mentioned.

Of these amine salts and phosphonium salts, tetramethylammonium chloride and butyltriphenylphosphonium thiocyanate are preferred. An amine salt and a phosphonium salt can be used individually or in mixture of 2 or more types. As content ratio of the amine salt and the phosphonium salt in the said coloring composition, 0.05 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] copolymers, and 0.1 mass part-5 mass parts are more preferable. By making the content rate of an amine salt and a phosphonium salt into the said specific range, the storage stability of the said coloring composition and low temperature baking can be compatible to a higher level.

[Amidine Salt]

As an amidine salt, at least 1 sort (s) chosen from the group which consists of a salt of the compound represented by following formula (7) can be used.

In said formula (7), m is an integer of 2-6. However, one part or all part of the hydrogen atom which an alkylene group has may be substituted by the organic group. Further, the alkylene group refers to, tetrahydro-pyrimidine in the alkylene group and the formula (7) in dinhwan (CH ₂₎ refers to an alkylene group both represented by _m.

As an organic group which the said alkylene group may have as a substituent, for example

Alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group and n-hexyl group;

Hydroxymethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxyisopropyl group, 3-hydroxy-t-butyl group, 6 C1-C6 hydroxyalkyl groups, such as a hydroxyhexyl group;

C2-C12 dialkylamino groups, such as a dimethylamino group, a methylethylamino group, a diethylamino group, a diisopropylamino group, a dibutylamino group, a t-butylmethylamino group, and a di-n-hexylamino group, etc. are mentioned.

Examples of the compound represented by the formula (7) include 1,5-diazabicyclo [4,3,0] -nonene-5 (DBN) and 1,5-diazabicyclo [4,4,0] -decene-5 , 1,8-diazabicyclo [5,4,0] -undecene-7 (DBU), 5-hydroxypropyl-1,8-diazabicyclo [5,4,0] -undecene-7, 5-dibutylamino-1,8-diazabicyclo [5,4,0] -undecene-7 and the like. Among these, DBN and DBU are preferable.

As an acid for the compound represented by said Formula (7) to form a salt, an organic acid and an inorganic acid are mentioned.

As an organic acid, a carbonic acid, a monoalkyl carboxylic acid, an aromatic hydroxy compound, sulfonic acid, etc. are mentioned, for example.

As carboxylic acid, for example

Saturated fatty acids such as formic acid, acetic acid, 2-ethylhexanoic acid and isovaleric acid;

Acrylic acid, crotonic acid, methacrylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, palmileic acid, oleic acid, linoleic acid, linoleic acid, baccenic acid, eleostearic acid, arachidonic acid, cinnamic acid, naphtha Unsaturated carboxylic acids such as tomic acid, benzoic acid and toluic acid;

Chloroacetic acid, cyanoacetic acid, dichloroacetic acid, trichloroacetic acid, trimethylacetic acid, fluoroacetic acid, bromoacetic acid, methoxyacetic acid, mercapto acetic acid, iodoacetic acid, vinylacetic acid, oxaloacetic acid, phenylacetic acid, phenoxyacetic acid Α substituted acetic acid such as;

Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, araze acid, suberic acid and sebacic acid;

Hydroxycarboxylic acids such as glycolic acid, lactic acid, citric acid, d-tinic acid, mesotinic acid, ascorbic acid and mandelic acid;

Ketocarboxylic acids such as pyrbic acid and levulinic acid;

And halocarboxylic acids such as 2-chloropropionic acid and 3-chloropropionic acid.

As monoalkyl carboxylic acid, methyl carbonic acid, ethyl carboxylic acid, etc. are mentioned, for example.

As an aromatic hydroxy compound, phenol, cresol, catechol, naphthol, etc. are mentioned, for example.

As sulfonic acid, octylbenzene sulfonic acid, butylbenzene sulfonic acid, toluene sulfonic acid, benzene sulfonic acid, methanesulfonic acid, etc. are mentioned, for example.

As an inorganic acid, for example

Halogen acids such as hydrochloric acid, hydrofluoric acid and bromic acid;

Carbonic acid; And

Perhalohydrogen acids, such as perchloric acid and perbromic acid, etc. are mentioned.

Among these acids, carbonic acid, aromatic hydroxy compound and sulfonic acid are preferable, saturated fatty acid, aromatic hydroxy compound and sulfonic acid are more preferable, sulfonic acid which is a strong acid is particularly preferable, and toluenesulfonic acid, methanesulfonic acid and octylbenzenesulfonic acid are most preferred. desirable. As an amidine salt, the salt of DBU and toluenesulfonic acid, the salt of DBU and octylbenzenesulfonic acid, the salt of DBN and toluenesulfonic acid, and the salt of DBN and octylbenzenesulfonic acid are preferable.

Amidine salt can be used individually or in mixture of 2 or more types. As a content rate of the amidine salt in the said coloring composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] copolymers, and 0.5 mass parts-5 mass parts are more preferable. By making the content rate of an amidine salt into the said specific range, the storage stability of the said coloring composition and low temperature baking can be compatible at a higher level.

[Amide compound]

As an amide compound, at least 1 sort (s) chosen from the group which consists of a compound which has an amide group represented by following formula (8)-(10) can be used.

In said formula (8), R <^31> and R <^32> is a hydrogen atom, a C1-C12 alkyl group, a cyclohexyl group, a phenyl group, a naphthyl group, a vinyl group, or 2-pyridyl group each independently. However, the said C1-C12 alkyl group, a phenyl group, and a naphthyl group may be substituted by the C1-C6 alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, or an acetyl group.

In said formula (9), R <^33> and R <^34> is a hydrogen atom, a C1-C12 alkyl group, or a cyclohexyl group each independently. A <^2> is a methylene group, a C2-C12 alkylene group, a phenylene group, a naphthylene group, or a vinylene group. However, the said methylene group, a C2-C12 alkylene group, a phenylene group, and a naphthylene group may be substituted by the C1-C6 alkyl group and a halogen atom.

In said formula (10), R <^35> and R <^36> is a hydrogen atom, a C1-C12 alkyl group, or a cyclohexyl group each independently. A <^3> is a methylene group, a C2-C12 alkylene group, a phenylene group, a naphthylene group, or a vinylene group. However, the said methylene group, a C2-C12 alkylene group, a phenylene group, and a naphthylene group may be substituted by the C1-C6 alkyl group and a halogen atom.

The amide compound represented by the formula (8) is a compound having one amide bond in the molecule. Specific examples thereof include acetamide, N-methylacetamide, N-ethylacetamide, Nn-propylacetamide, N-isopropylacetamide, Nn-butylacetamide, N-isobutylacetamide, and Nt- Butylacetamide, Nn-hexylacetamide, Nn-octylacetamide, Nn-dodecylacetamide, propionylamide, butyrylamide, valerylamide, isovalerylamide, octanoylamide, acetanilide, acetoacetanilide , o-acetamidebenzoic acid, m-acetamidebenzoic acid, p-acetamidebenzoic acid, o-acetamidephenol, m-acetamidephenol, p-acetamidephenol, acetamidenaphlenene, phthalamide acid, acrylamide, benz Amide, naphthoamide, nicotinamide, isonicotinamide, and the like.

Among these, acetamide, N-methylacetamide, and phthalamic acid are preferable from the viewpoint of improving storage stability at room temperature, heat resistance such as colored patterns obtained, voltage holding ratio and the like.

The compounds represented by the formulas (9) and (10) are compounds having two amide bonds in the molecule. Specific examples thereof include phthalamide, isophthalamide, terephthalamide, malonamide, succinamide, glutaramide, adiphamide, pimelineamide, subvertamide, azelaamide, sebacamide, maleamide, Fumaramide, N, N'-dimethyl-phthalamide, N, N'-dimethyl-isophthalamide, N, N'-dimethyl-terephthalamide, N, N'-diacetyl-o-phenylenediamine, N, N'-diacetyl-m-phenylenediamine, N, N'-diacetyl-p-phenylenediamine, N, N'-dipropionyl-o-phenylenediamine, N, N'-dipropionyl- m-phenylenediamine, N, N'-dipropionyl-p-phenylenediamine, N, N'-diacetyl-ethylenediamine, N, N'-diacetyl-propylenediamine, N, N'-diacetyl -Butylenediamine, N, N'-diacetyl-hexamethylenediamine, N, N'-diacetyl-dodecylmethylenediamine, N, N'-dibenzoyl-ethylenediamine, N, N'-dibenzoyl-propylene Diamine, N, N'-dibenzoyl-butylenediamine, N, N'-diben Mono-hexamethylenediamine, N, N'-dibenzoyl-dodecylmethylenediamine, N, N'- dinaphthoyl-ethylenediamine, N, N'- dinaphthoyl-propylenediamine, N, N'- dinaphtho Mono-butylenediamine, N, N'- dinaphthoyl-hexamethylenediamine, N, N'- dinaphthoyl-dodecylmethylenediamine, etc. are mentioned.

Among them, isophthalamide, adiphamide, N, N'-diacetyl-p-phenylenediamine, N, N'-diacetyl-hexa from the viewpoint of achieving both high storage stability and low temperature calcining at a high level. Methylenediamine is preferred.

The amide compounds may be used alone or in combination of two or more. As a content rate of the amide compound in the said coloring composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] copolymer, and 0.5 mass part-5 mass parts are more preferable. By making the content rate of an amide compound into the said specific range, the storage stability of the said coloring composition and low temperature baking can be compatible at a higher level.

[Thiol Compound]

The thiol compound is a compound having two or more mercapto groups in one molecule. Although the thiol compound is not specifically limited as long as it has two or more mercapto groups in 1 molecule, At least 1 sort (s) chosen from the group which consists of a compound represented by following formula (11) can be used.

In the formula (11), R ³⁷ is an alkylene group of a methylene group, having 2 to 10 carbon atoms. However, some or all of the hydrogen atoms in these groups may be substituted by the alkyl group. Y ¹ is a single bond, -CO-, or -O-CO- ^* . Provided that a bond attached with * binds to R ³⁷ . n is an integer of 2-10. A <^4> is a C2-C70 n-valent hydrocarbon group which may have one or more ether bonds, or group represented by following formula (12) when n is 3.

In said formula (12), R <^38> -R <^40> is a methylene group or a C2-C6 alkylene group each independently. "*" Represents a bond.

As the compound represented by the formula (11), typically, an esterified product of mercaptocarboxylic acid and a polyhydric alcohol can be used. Examples of the mercaptocarboxylic acid constituting the esterified product include thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, and 3-mercaptopentanoic acid. Moreover, as polyhydric alcohol which comprises esterified product, ethylene glycol, propylene glycol, trimethylol propane, pentaerythritol, tetraethylene glycol, dipentaerythritol, 1, 4- butanediol, pentaerythritol, etc. are mentioned, for example. have.

As a compound represented by said Formula (11), trimethylol propane tris (3-mercapto propionate), pentaerythritol tetrakis (3-mercapto propionate), and tetra ethylene glycol bis (3- mercapto propio) Nate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetra Keith (3-mercaptobutylate), pentaerythritol tetrakis (3-mercaptopentylate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- 2,4,6 (1H, 3H, 5H) -trione is preferred.

As a compound which has two or more mercapto groups in 1 molecule of a thiol compound, the compound represented by following formula (13)-formula (15) can also be used.

In said formula (13), R <^41> is a methylene group or a C2-C20 alkylene group. R <^42> is a methylene group or a C2-C6 linear or branched alkylene group. k is an integer of 1-20.

In said formula (14), R <^43> -R <^46> is group represented by a hydrogen atom, a hydroxyl group, or following formula (15) each independently. However, at least 1 of R <^43> -R <^46> is group represented by following formula (15).

In said formula (15), R ⁴⁷ is a methylene group or a C2-C6 linear or branched alkylene group.

The thiol compounds may be used alone or in combination of two or more. As a content rate of the thiol compound in the said coloring composition, 1 mass part-20 mass parts are preferable with respect to 100 mass parts of [A] copolymers, and 5 mass parts-15 mass parts are more preferable. By making the content rate of a thiol compound into the said specific range, the storage stability of the said coloring composition and low temperature baking can be compatible to a higher level.

[Block isocyanate compound]

The block isocyanate compound is made to be inert at room temperature by reacting an isocyanate group with an active hydrogen group-containing compound (blocking agent). When the isocyanate group is heated, the blocking isocyanate compound has a property that the isocyanate group is regenerated. When the coloring composition contains blocked isocyanate, the isocyanate-hydroxyl group crosslinking reaction proceeds as an effective crosslinking agent, so that the storage stability of the coloring composition and low temperature calcining can be achieved at a high level.

The block polyisocyanate compound is obtained by a known reaction between a polyisocyanate derived from an aliphatic or alicyclic diisocyanate and a compound having an active hydrogen (block).

Examples of the diisocyanate include tetramethylene diisocyanate, pentane diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethyl-1,6-diisocyanate hexane, 2,4,4-trimethyl-1, 6-diisocyanate, lysine diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis (isocyanatomethyl) cyclohexane, 4,4-dicyclohexyl methane diisocyanate, norbornene diisocyanate, tolylene di Isocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xyldine isocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6 -Hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl diisocyanate, etc. are mentioned.

As a commercially available product, for example,

As an isocyanate group blocked by the oxime of methyl ethyl ketone, duranate copper TPA-B80E, copper TPA-B80X, copper E402-B80T, copper MF-B60XN, copper MF-B60X, copper MF-B80M (above, Asahi Kasei Co., Ltd.) Co., Ltd.);

As an isocyanate group blocked with active methylene, Duranate MF-K60X (Asahi Kasei Co., Ltd.);

As a block body of the isocyanate compound which has a (meth) acryloyl group, Karenz MOI-BP and Karenz MOI-BM (above, Showa Denko KK) are mentioned. Among these, when duranate E402-B80T and copper MF-K60X are used, high flexibility is expressed, and since the hardness can be freely controlled by using it as a mixing system with another, it is preferable.

As polyisocyanate derived from diisocyanate, isocyanurate type polyisocyanate, biuret type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, etc. are mentioned, for example. From the viewpoint of curability, isocyanurate type polyisocyanate is preferable.

Examples of the blocking agent include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, pyrazole compounds, urea compounds, and oximes. A compound, an amine compound, an imine compound, a pyridine compound, etc. are mentioned.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol and the like;

As a phenol type compound, For example, phenol, cresol, ethyl phenol, butyl phenol, nonyl phenol, dinonyl phenol, styrenated phenol, hydroxy benzoic acid ester, etc .;

As an active methylene compound, For example, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetic acid, acetylacetone, etc .;

As a mercaptan type compound, For example, butyl mercaptan, dodecyl mercaptan, etc .;

Examples of the acid amide compound include acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, and the like;

As an acid imide type compound, For example, succinic acid imide, maleic acid imide, etc .;

As an imidazole compound, For example, imidazole, 2-methylimidazole, etc .;

As a pyrazole type compound, 3-methylpyrazole, 3, 5- dimethyl pyrazole, 3, 5- ethyl pyrazole, etc .;

As a urea type compound, For example, urea, thiourea, ethylene urea, etc .;

As an oxime type compound, For example, formaldehyde oxime, acetaldooxime, acetoxime, methyl ethyl keto oxime, cyclohexanone oxime, etc .;

As an amine compound, For example, diphenylamine, aniline, carbazole, etc .;

As an imine type compound, Ethylenimine, a polyethyleneimine, etc .;

As a pyridine type compound, 2-hydroxypyridine, 2-hydroxyquinoline, etc. are mentioned, for example.

Block isocyanate compounds can be used individually or in mixture of 2 or more types. As content rate of the block isocyanate compound in the said coloring composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] copolymer, and 0.5 mass part-5 mass parts are more preferable. By making the content rate of a block isocyanate compound into the said range, the storage stability of the said coloring composition and low temperature baking can be compatible to a higher level.

[Imidazole ring containing compound]

As an imidazole ring containing compound, at least 1 sort (s) chosen from the group which consists of a compound represented by following formula (16) can be used.

In said Formula (16), A <^5> , A <^6> , A <^7> and R <^48> are C1-C20 linear, branched, or cyclic hydrocarbon group which may respectively independently have a hydrogen atom or a substituent. A ⁶ and A ⁷ may be connected to each other to form a ring.

As a C1-C20 linear, branched or cyclic hydrocarbon group which A <^5> , A <^6> , A <^7> and R <^48> represent, for example

Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -Octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n- C1-C20 alkyl groups, such as a heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-eicosyl group;

Cycloalkyl groups having 3 to 20 carbon atoms such as a cyclopentyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;

C6-C20 aryl groups, such as a phenyl group, toluyl group, benzyl group, methyl benzyl group, xylyl group, mesityl group, naphthyl group, and anthyl group;

Condensed alicyclic hydrocarbon groups having 6 to 20 carbon atoms such as norbornyl group, tricyclodecaneyl group, tetracyclododecyl group, adamantyl group, methyl adamantyl group, ethyl adamantyl group, and butyl adamantyl group Can be mentioned.

The hydrocarbon group may be substituted, and as a specific example of this substituent,

Hydroxyl group;

Carboxyl groups;

Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group C1-C4 hydroxyalkyl groups, such as a 3-hydroxybutyl group and 4-hydroxybutyl group;

C1-C4 alkoxyl groups, such as a methoxyl group, an ethoxyl group, n-propoxyl group, i-propoxyl group, n-butoxyl group, 2-methylpropoxyl group, 1-methylpropoxyl group, t-butoxyl group, etc. ;

Cyano;

Cyanoalkyl groups having 2 to 5 carbon atoms such as cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, and 4-cyanobutyl group;

Alkoxycarbonyl groups having 2 to 5 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and t-butoxycarbonyl group;

Alkoxycarbonylalkoxy groups having 3 to 6 carbon atoms, such as a methoxycarbonyl methoxyl group, an ethoxycarbonyl methoxyl group, and a t-butoxycarbonyl methoxyl group;

Halogen atoms such as fluorine and chlorine;

Fluoroalkyl groups, such as a fluoromethyl group, a trifluoromethyl group, and a pentafluoroethyl group, etc. are mentioned.

As said ring formed by connecting A <^6> and A <^7> mutually, Preferably, an aromatic ring and the C2-C20 saturated or unsaturated nitrogen containing heterocycle are mentioned. As an imidazole ring containing compound in the case where the ring which A <^6> and A <^7> connects and mutually forms in the case of a benzene ring, the compound represented by following formula (17) is mentioned.

In said formula (17), R <^48> and A <^5> is synonymous with said formula (16). R ⁴⁹ to R ⁵² are each independently a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Moreover, as a hydrocarbon group represented by R <^49> -R <^52> , the same thing as the hydrocarbon group in said Formula (16) is mentioned.

As the imidazole ring-containing compound, 2-phenylbenzimidazole, 2-methylimidazole, and 2-methylbenzimidazole are preferable. The imidazole ring-containing compounds may be used alone or in admixture of two or more. As a content rate of an imidazole ring containing compound, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] copolymer, and 0.5 mass part-5 mass parts are more preferable. By making the content rate of an imidazole ring containing compound into the said specific range, the storage stability of the said coloring composition and low temperature baking can be compatible at a higher level.

<[F] Copolymer>

The copolymer which has the [F] radical reactive functional group which the said coloring composition can contain suitably is the copolymer which can be synthesize | combined using 1 or more types of the above-mentioned (A1) compound which gives a carboxyl group containing structural unit (following) And "[F] copolymer") and the above-mentioned (A2) compound giving an epoxy group containing structural unit can be reacted and synthesize | combined.

The structural unit which has a (meth) acryloyl group which a [F] copolymer contains is represented by following formula (18). This structural unit is obtained by reacting the carboxyl group in the [F] copolymer derived from the compound (A1) with the epoxy group of the compound (A2) to form an ester bond.

In said formula (18), R ⁵³ is a hydrogen atom or a methyl group. t is an integer of 1-6. A ⁸ is a divalent group represented by the following formula (18-1) or (18-2).

In said formula (18-1), R <^54> is a hydrogen atom or a methyl group. In Formulas (18-1) and (18-2), the bond of * is bonded to an oxygen atom.

When the structural unit represented by said formula (18) reacts compounds, such as glycidyl methacrylate and 2-methylglycidyl methacrylate, as a (A2) compound with the copolymer which has a carboxyl group, for example. , A ⁸ in formula (18) becomes formula (18-1). On the other hand, when a compound such as methacrylic acid 3,4-epoxycyclohexylmethyl is reacted as the (A2) compound, A ⁸ in Formula (18) becomes Formula (18-2).

About the detail of a (A1) compound and a (A2) compound, since the thing similar to what was illustrated by the term of the said [A] copolymer is mentioned, description is abbreviate | omitted here.

In the synthesis | combination of [F] copolymer, you may use compounds other than the (A1) compound, for example, the above-mentioned (A3) compound, (A4) compound, etc. as a copolymerization component. About the detail of a (A3) compound and a (A4) compound, the thing similar to what was illustrated by the term of the above-mentioned [A] copolymer is mentioned. These compounds include methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] methacrylic acid, Octane, decane-8-yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, and 1,3-butadiene.

As a method of copolymerization of the [F] copolymer, the method of superposing | polymerizing (A1) compound and (A3) compound etc. as needed using a radical polymerization initiator in a solvent is mentioned, for example. As a radical polymerization initiator, the thing similar to what was illustrated by the term of the above-mentioned [A] copolymer is mentioned. As a usage-amount of a radical polymerization initiator, it is 0.1 mass%-50 mass% normally with respect to 100 mass% of polymerizable unsaturated compounds, Preferably they are 0.1 mass%-20 mass%. [F] copolymer may be used for manufacture of [F] copolymer as a polymerization reaction solution, and may be used for manufacture of [F] copolymer after separating a copolymer from a solution once.

In the said polymerization reaction, in order to adjust molecular weight, a molecular weight modifier can be used. As a molecular weight modifier, the same thing as what was illustrated by the term of the above-mentioned [A] copolymer is mentioned. Moreover, polymerization temperature is 0 degreeC-150 degreeC normally, Preferably it is 50-120 degreeC, and polymerization time is 10 minutes-20 hours normally, Preferably it is 30 minutes-6 hours.

As Mw of the [F] copolymer, 2,000-100,000 are preferable and 5,000-50,000 are more preferable. By setting Mw to 2,000 or more, not only a sufficient development margin of a coloring composition is obtained, but also the fall of the residual film ratio (ratio in which a pattern-shaped thin film is appropriately remained) of the coating film formed is prevented, and also the shape of a pattern obtained, heat resistance, etc. Can be kept good. On the other hand, by setting Mw to 100,000, high sensitivity can be preserved and a good pattern shape can be obtained. Moreover, as molecular weight distribution (Mw / Mn) of a [F] copolymer, 5.0 or less are preferable and 3.0 or less are more preferable. By making Mw / Mn 5.0 or less, the shape of the spacer pattern obtained can be kept favorable. Moreover, the coloring composition containing the [F] copolymer which has Mw / Mn of the said specific range has high developability, and can develop a predetermined pattern shape easily, without developing image development residue in a image development process. Can be.

Examples of the solvent used for the polymerization reaction include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyls. Ether propionate, aromatic hydrocarbons, ketones, other esters, etc. are mentioned.

As content rate of the structural unit derived from the (A1) compound of the [F] copolymer, 5 mass%-60 mass% are preferable, 7 mass%-50 mass% are more preferable, 8 mass%-40 mass% Particularly preferred. By setting the content rate of the structural unit derived from the compound (A1) in the above range, a colored composition in which various properties such as developability and storage stability are balanced to a higher level is obtained.

As content rate of structural units derived from compounds, such as (A3) compounds and (A4) compounds, other than the (A1) compound of [F] copolymer, they are 10 mass%-90 mass%, 20 mass%-80 mass%. By making the content rate of such a structural unit into the said range, control of the molecular weight of a copolymer becomes easy and the coloring composition which the balance of developability, a sensitivity, etc. to a higher level is obtained.

In the reaction between the [F] copolymer and the compound (A2), an unsaturated compound having an epoxy group is preferably added to a solution of a copolymer containing a polymerization inhibitor, in the presence of a suitable catalyst, if necessary. Stir for a predetermined time while warming. As said catalyst, tetrabutylammonium bromide etc. are mentioned, for example. As said polymerization inhibitor, p-methoxy phenol etc. are mentioned, for example. As reaction temperature, 70 degreeC-100 degreeC is preferable. As reaction time, 8 hours-12 hours are preferable.

As a usage ratio of (A2) compound, 10 mass%-99 mass% are preferable with respect to the carboxyl group derived from the (A2) compound in a copolymer, and 5 mass%-97 mass% are more preferable. By making the use ratio of a (A2) compound into the said range, the reactivity with a copolymer, the heat resistance of a coloring composition, etc. improve more. (A2) may be used alone or in admixture of two or more.

As content rate of the structural unit which has a radical reactive functional group in [F] copolymer, 5 mass%-60 mass% are preferable, 7 mass%-50 mass% are more preferable, 8 mass%-40 mass% Particularly preferred.

As a use ratio of the copolymer which has a [F] radical reactive functional group in the said coloring composition, 1 mass part-90 mass parts are preferable with respect to 100 mass parts of [A] copolymers, and 5 mass parts-70 mass parts are more preferable. Do. By making the use ratio of the copolymer which has a [F] radical reactive functional group into the said range, the said coloring composition can form the coloring pattern etc. which have sufficient heat resistance, solvent resistance, and voltage hold ratio even in low exposure amount.

&Lt; Other optional components >

The coloring composition is in addition to the above-mentioned [A] copolymer, the [B] polymerizable compound, the [C] polymerization initiator, the [D] coloring agent, the [E] curing agent, and the [F] copolymer which is a suitable component, Other arbitrary components, such as surfactant, a storage stabilizer, an adhesion | attachment adjuvant, a heat resistance improver, etc. can be contained as needed in the range which does not impair an effect. These arbitrary components may be used independently, or may mix and use 2 or more types. Hereinafter, each component will be described in detail.

[Surfactants]

Surfactant can be used in order to improve the film formation property of a coloring composition further. As surfactant, a fluorochemical surfactant, silicone type surfactant, and other surfactant are mentioned, for example.

As a fluorine type surfactant, the compound which has a fluoroalkyl group and / or a fluoroalkylene group in at least any part of terminal, 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 (fluoroalkyl poly Oxyethylene ether), fluoroalkyl ammonium iodine, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carboxylic acid fluoroalkyl ester, etc. Can be.

As a commercial item of a fluorine-type surfactant, BM-1000, BM-1100 (above, BM, CHEMIE company), Megaface F142D, copper F172, copper F173, copper F183, copper F178, copper F191, copper F471, East F476 (above, Dai Nippon Inkika Chemical Co., Ltd.), Fluorad FC-170C, East-171, East-430, East-431 (above, Sumitomo 3M Kabuki Kaisha), Supron S -112, East-113, East-131, East-141, East-145, East-382, Suflon SC-101, East-102, East-103, East-104, East-105, East- 106 (above, Asahi Glass Co., Ltd.), Ftop EF301, east 303, east 352 (above, Shin Akita Kasei Co., Ltd.), Fgentgent FT-100, East-110, East- 140A, copper-150, copper-250, copper-251, copper-300, copper-310, copper-400S, Pleasant FTX-218, copper-251 (above, Neos Co., Ltd.), etc. are mentioned.

As a commercial item of a silicone type surfactant, Toray silicone 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, Torre 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 surfactants, such as polyoxyethylene dialkyl esters, such as polyoxyethylene dilaurate and polyoxyethylene distearate, (meth) acrylic-acid copolymer polyflow No. 57, No. 95 (above, Kyoeisha Chemical Co., Ltd.) etc. are mentioned.

As the usage-amount of surfactant, 1.0 mass part or less is preferable with respect to 100 mass parts of [A] copolymers, and 0.7 mass part or less is more preferable. When the usage-amount of surfactant exceeds 1.0 mass part, it becomes easy to produce a film stain.

[Storage stabilizer]

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitroso compounds, and the like, and more specifically 4-methoxyphenol and N-nitroso-N-phenyl Hydroxylamine aluminum etc. are mentioned.

As the usage-amount of a storage stabilizer, 3.0 mass parts or less are preferable with respect to 100 mass parts of [A] copolymers, and 1.0 mass part or less is more preferable. When the compounding quantity of a storage stabilizer exceeds 3.0 mass parts, a sensitivity may fall and a pattern shape may deteriorate.

[Adhesive preparation]

An adhesion | attachment adjuvant can be used in order to improve the adhesiveness of the coloring pattern and color filter which are obtained, and a board | substrate further. As an adhesion | attachment adjuvant, the functional silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an oxiranyl group, is preferable, For example, trimethoxysilyl benzoic acid, (gamma)-methacryloxypropyl Trimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, etc. are mentioned.

As the usage-amount of an adhesion | attachment adjuvant, 20 mass parts or less are preferable with respect to 100 mass parts of [A] copolymers, and 15 mass parts or less are more preferable. When the usage-amount of an adhesion | attachment adjuvant exceeds 20 mass parts, there exists a tendency which develops a developing residue easily.

[Heat resistance improver]

Examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds, N- (alkoxymethyl) melamine compounds, and the like.

Examples of the N- (alkoxymethyl) glycoluril compound include N, N ', N ", N"'-tetra (methoxymethyl) glycoluril, N, N, N ', N'-tetra (ethoxymethyl Glycoluril, 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, etc. are mentioned. Of these N- (alkoxymethyl) glycoluril compounds, N, N, N ', N'-tetra (methoxymethyl) glycoluril are preferred.

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 Co., Ltd.), etc. are mentioned, for example.

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

&Lt; Preparation method of colored composition >

The coloring composition of this invention is a [A] copolymer, a [B] polymeric compound, a [C] polymerization initiator, a [D] coloring agent, a [E] hardening | curing agent, a [F] copolymer which is a suitable component, and other as needed. It is prepared by mixing arbitrary components uniformly. This coloring composition, Preferably, it melt | dissolves in a suitable solvent and is used in solution form.

As a solvent used for preparation of the said coloring composition, an essential component and arbitrary components are melt | dissolved uniformly, and what does not react with each component is used. As such a solvent, the same thing as what was illustrated as a solvent which can be used for manufacturing the above-mentioned [A] copolymer is mentioned.

Among these solvents, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol from the viewpoint of solubility of each component, reactivity with each component, ease of film formation, and the like. 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, di Propylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol No methyl ether, tripropylene glycol monoethyl ether and (poly) alkylene glycol monoalkyl ether;

Acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid ethylene glycol mono-n-propyl ether, acetic acid ethylene glycol mono-n-butyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, 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, Acetic acid (poly) alkylene glycol monoalkyl ethers such as methoxybutyl;

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

Methylhexanone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan- Ketones;

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, propylene glycol monomethyl ether, propylene glycol monoethyl ether, from the viewpoint of solubility, pigment dispersibility, coating properties, 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, with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, oxalic acid di High boiling point solvents, such as ethyl, diethyl maleate, (gamma) -butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate, can also be used together. The said high boiling point solvent can be used individually or in combination of 2 or more types. have.

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% to 40 mass% is more preferable. When preparing the said coloring composition in 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. %). Although more preferable solid content concentration changes with the formation method of the 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.

<Coloring pattern, color filter, and manufacturing method thereof>

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

(1) Process of forming the coating film of the said coloring composition on a board | substrate (Hereinafter, it may be called "(1) process.),

(2) Process of forming colored pattern in the said coating film (Hereinafter, it may be called "(2) process"),

(3) It has the process (Hereinafter, it may call a "(3) process") of baking the coating film in which the said coloring pattern was formed at 200 degrees C or less.

By the manufacturing method of the color filter of this invention using the said coloring composition, the color filter with favorable heat resistance, chemical-resistance, voltage holding ratio, etc. can be formed. In addition, as mentioned above, since the said coloring composition contains a specific component, low temperature baking can be implement | achieved and baking at the temperature of 200 degrees C or less in the said process (3) becomes possible. Therefore, the color filter manufactured in this way is suitable for the flexible display in which low temperature baking is desired. Hereinafter, each process is explained in full detail.

[(1) Process]

In this process, the coating film of the said coloring composition is formed 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. Subsequently, after apply | coating the said coloring composition containing a red [D] 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, or 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 larger than that of the black matrix because the partition wall 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. If desired, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, or the like. .

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 for 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.

[(2) Process]

In this step, the coating film formed in step (1) is exposed through a photomask, developed using an alkaline developer, and the unexposed portions of the coating film are dissolved and removed to form a red pixel pattern in a predetermined arrangement. Arranged pixel arrays are formed to obtain a coloring pattern.

Subsequently, using each green or blue coloring composition, process (1) and process (2) are repeated, and a green pixel array and a blue pixel array are sequentially formed on the same board | substrate. Thereby, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in this invention, the order 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 as described above. It can form similarly to the case of formation of a pixel.

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 lasers. Laser light sources, such as these, etc. are mentioned. Radiation in the range of 190 nm-450 nm is preferable. As for the 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, it washes with water normally. As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle developing method and the like can be applied. As image development conditions, 5 second-300 second are preferable at normal temperature.

[(3) Process]

After forming a coloring pattern at the process (2), baking (postbaking) is performed and hardening a coloring pattern can manufacture a color filter. It is 200 degrees C or less as heating conditions of postbaking. The heating time of the postbaking is from 10 minutes to 60 minutes. In this invention, even if the postbaking temperature is low temperature, the coloring pattern which is excellent in solvent resistance etc. 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, 0.5 micrometer-5.0 micrometers, 1.0 micrometer-3.0 micrometers are preferable normally. Moreover, in order to raise hardness etc. to the level which is actually required commercially, the baking process at the temperature exceeding 120 degreeC is normally needed.

<Color display element>

The color display element of this invention is equipped with the color filter formed from the said coloring composition. 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)

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is described based on an Example, this invention is not limitedly interpreted by this Example.

<Synthesis of [A] Copolymer>

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 (A1) compound, 40 parts by mass of glycidyl methacrylate as the (A2) compound, 20 parts by mass of styrene as the (A4) compound and methacrylic acid tricyclo [5.2.1.0 ^{2, 6} ] 28 parts by mass of decan-8-yl was added, nitrogen was substituted, and the temperature of the solution was increased to 70 ° C. with gentle stirring, and the copolymer (A-1) was preserved for 5 hours to polymerize. The solution containing was obtained. Solid content concentration of the obtained polymer solution was 31.3%, and Mw of the copolymer (A-1) 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 (A1) compound, 14 parts by mass of 2-methylglycidyl methacrylic acid as the (A2) compound, 20 parts by mass of glycidyl methacrylate, and 10 parts by mass of styrene as the (A4) compound 23 parts by mass of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl and 15 parts by mass of methyl methacrylate were added thereto, and after nitrogen-substituting, the temperature of the solution was adjusted to 70 ° C. with gentle stirring. The solution containing the copolymer (A-2) was obtained by raising 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-2) was 10,100.

[Synthesis Example 3]

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 3-methoxybutyl acetate were placed. Subsequently, 18 parts by mass of methacrylic acid as the (A1) compound, 30 parts by mass of methacrylic acid 3,4-epoxycyclohexyl methyl as the (A2) compound, and 6 parts by mass of 4-hydroxyphenyl methacrylate as the (A3) compound. And (A4) 10 mass parts of styrene and 36 mass parts of benzyl methacrylate as a compound, and while stirring gently, the temperature of a solution is raised to 80 degreeC, this temperature is preserve | saved and maintained for 5 hours, and a copolymer (A A solution containing -3) was obtained. Solid content concentration of the obtained polymer solution was 30.9%, and Mw of the copolymer (A-3) was 9,800.

<Synthesis of [F] Copolymer>

[Synthesis Example 4]

In a flask equipped with a cooling tube and a stirrer, 4 parts by mass of AIBN and 300 parts by mass of diethylene glycol methylethyl ether were added, followed by 23 parts by mass of methacrylic acid as the (A1) compound, and 10 parts by mass of styrene as the (A4) compound. 32 parts by mass of benzyl acrylate and 35 parts by mass of methyl methacrylate were added thereto, and then 2.7 parts by mass of α-methylstyrene dimer was added and the temperature of the solution was raised to 80 ° C. with gentle stirring, and the temperature was maintained for 4 hours. Thereafter, the mixture was raised to 100 ° C, and this solution was maintained for 1 hour to polymerize to obtain a solution containing the copolymer (F-1). Solid content concentration of the obtained polymer solution was 24.9%, and Mw was 12,500. Subsequently, 1.1 mass part of tetrabutylammonium bromide and 0.05 mass part of 4-methoxy phenols were added to the solution containing the obtained copolymer as a polymerization inhibitor, and it stirred for 30 minutes at 90 degreeC in air atmosphere, and then used as a (A2) compound. Copolymer (F-1) was obtained by making 16 mass parts of glycidyl crylates, and making it react for 90 hours with 90 degreeC. Solid content concentration of the obtained polymer solution was 29.0%, and Mw was 14,200.

[Comparative Synthesis Example 1]

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

&Lt; Preparation of colored composition >

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

Each component of the kind and compounding quantity which are shown in Table 1 was mixed, and after adding a solvent so that solid content concentration might be 30 mass%, the coloring composition was prepared by 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.

The detail of each component used for preparation of the coloring composition shown in Table 1 is shown below.

&Lt; [B] Polymerizable compound >

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

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

B-3: 1,9-nonanediol diacrylate

B-4: pentaerythritol tetraacrylate

B-5: trimethylolpropane triacrylate

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

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

B-8: ethylene oxide modified dipentaerythritol hexaacrylate

<[C] polymerization initiator>

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

C-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (irgacure OXE02, Chiba specialty Chemicals Co., Ltd.

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

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

<[D] colorant>

D-1: C.I. Solvent Red 45

D-2: C.I. Solvent Yellow 98

D-3: C.I. Solvent Blue 67

D-4: C.I. Solvent Yellow 82

D-5: C.I. Solvent Blue 35

D-6: C.I. Solvent Blue 59

D-7: Valifast yellow 1101

D-8: C.I. Acid Black 24

<[E] Curing Agent>

E-1: trioctylamine

E-2: 2-phenylbenzoimidazole

E-3: Tetramethylammonium Chloride

E-4: Butyl triphenyl phosphonium thiocyanate

E-5: toluenesulfonate of 1,8-diazabicyclo [5,4,0] -undecene-7 (DBU)

E-6: N, N'-diacetyl-p-phenylenediamine

E-7: pentaerythritol tetrakis (3-mercaptopropionate)

E-8: TPA-B80E (Asahi Kasei Chemicals Co., Ltd., HDI type block isocyanate, solid content 80%, effective isocyanate content 12.3%)

E-9: 4,4'-diaminodiphenyl sulfone

E-10: 3-aminobenzenesulfonic acid ethyl

e-1: octylamine

<Synthesis of [F] Copolymer>

F-1: copolymer of methacrylic acid / styrene / benzyl methacrylate / methyl methacrylate

<Solvent>

S-1: Propylene Glycol Monomethyl Ether Acetate

S-2: cyclohexanone

S-3: ethyl lactate

<Evaluation>

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

[Measurement of Preservation Stability]

The obtained coloring composition was left to stand in 40 degreeC oven for 1 week, the viscosity before and behind heating was measured, and the viscosity change rate (%) was calculated | required. At this time, the viscosity change rate was made into storage stability, and when it was 5% or less, it was judged that storage stability is favorable, and when it exceeds 5%, it was judged that storage stability is poor. The viscosity was measured at 25 degreeC using the E-type viscosity meter (VISCONIC® ELD.R, Toki Sangyo Co., Ltd.).

<Formation of Colored Pattern>

On the soda glass substrate SiO ₂ film is formed to prevent the elution of sodium ions on the surface, the examples and comparative examples the coloring composition, was applied using a spin coater. Subsequently, prebaking was performed by the 90 degreeC hotplate for 2 minutes, 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>), 300 (J / m <2>) of the 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, It exposed at the exposure amount of 500 (J / m <2>), 700 (J / m <2>), and 1,000 (J / m <2>). 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 these substrates to form a shower image on the substrate. A coloring pattern was formed. Furthermore, it post-baked at 180 degreeC for 30 minutes, and formed the coloring pattern.

<Evaluation>

The following evaluation was performed about the produced coloring pattern. The results are shown together in Table 1.

[Measurement of developing resistance]

In the formation of the coloring pattern, the following formula:

Film thickness ratio before and after development = (film thickness after development / film thickness before development) × 100

When the value of is 95% or more, "A" (good judgment), when less than 95% or when a defect is recognized in a part of the coloring pattern "B" (judged to be slightly defective), the pattern is all peeled off from the substrate Case was made into "C" (judged to be defective).

[Measurement of heat resistance]

In formation of the said coloring pattern, it operated similarly except having exposed with the exposure amount of 1,000 (J / m <2>), and formed the coloring pattern. 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).

[Measurement of Solvent Content]

In the formation of the colored pattern, a colored pattern was produced in the same manner except that the exposure was performed at an exposure amount of 1,000 (J / m 2). This board | substrate was immersed for 30 minutes in 60 degreeC N-methylpyrrolidone. The color pattern is preserve | saved after immersion, and when N-methylpyrrolidone after immersion is not colored at all, it is "A" (determined as good), and N-methyl after immersion of the color pattern preserved after immersion. The case where pyrrolidone 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). Judgment).

[Measurement of Voltage Integrity]

A SiO ₂ film was formed on the surface to prevent elution of sodium ions, and after spin coating the colored composition onto a soda glass substrate on which an ITO (indium tin oxide alloy) electrode was deposited in a predetermined shape, Prebaking was performed for 10 minutes in the clean oven, and the coating film of 2.0 micrometers in thickness was formed.

Subsequently, it exposed to the coating film by the exposure amount of 500 J / m <2> without interposing a photo mask. 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 wash | cleaned with ultrapure water, air-dried, and post-baked at 180 degreeC for 60 minutes, and hardened 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 60 degreeC thermostat, 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). At this time, the applied voltage was 5.5V square wave and the measurement frequency was 60Hz. Here, the voltage holding ratio is the following formula:

(Voltage applied in liquid crystal cell potential difference / 0 millisecond after 16.7 milliseconds) * 100

Is the value of. If the voltage holding ratio of the liquid crystal cell is less than 90%, it means that the liquid crystal cell cannot keep the applied voltage at a predetermined level for a time of 16.7 milliseconds, and cannot align the liquid crystal sufficiently, and burn-in such as afterimage There is a high possibility of causing.

<Production of Color Filters>

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

Next, it operated similarly and the green stripe-shaped pattern was formed using the coloring composition of Example 4. Moreover, the blue stripe pattern was formed using the coloring composition of Example 5, and the stripe color filter (stripe width 100 micrometers) of three colors of red, green, and blue was formed. The colored patterns of three colors of red, green, and blue formed under the conditions of the above-described post-baking temperature of 180 ° C. and 30 minutes do not cause problems such as defects in the pattern due to insufficient curing and peeling from the substrate. Three-color stripe-shaped color filters 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 (flatness) of the surface of a protective film was measured by the contact type film thickness measuring apparatus (alpha) -step (Tenco Japan Corporation) (measurement length 2,000 micrometers, measurement range 2,000) Μm angle, the measured number n = 5). That is, the measurement direction is made into two directions of the stripe line short axis direction in the red, green, and blue directions and the stripe line major axis direction of the same color of red, red, green, green, and blue 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 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 were 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 in 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 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 tolerance, heat resistance, solvent resistance, voltage retention, etc. are obtained. Therefore, the said coloring composition is suitable for preparation 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 color filters for flexible displays, such as an electronic paper. Can be used.

Claims (7)

[A] A copolymer having a (A1) carboxyl group-containing structural unit and (A2) epoxy group-containing structural unit,
[B] a polymerizable compound having an ethylenically unsaturated bond,
[C] radiation sensitive polymerization initiator,
[D] colorants,
[E] Compound represented by the following formula (1), compound represented by the following formula (2), tertiary amine compound, amine salt, phosphonium salt, amidine salt, amide compound, thiol compound, blocked isocyanate compound and imidazole ring-containing At least one curing agent selected from the group consisting of compounds, and
[F] a coloring composition containing a copolymer having a radical reactive functional group:

(In formula (1), R <^1> -R <^6> is a hydrogen atom, an electron withdrawing group, or an amino group each independently, provided that at least one of R <^1> -R <^6> is an electron withdrawing group, and in R <^1> -R <^6> At least one is an amino group, and all or part of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms;
In the formula (2), R ⁷ to R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group or an amino group; Provided that at least one of R ⁷ to R ¹⁶ is an amino group; Moreover, all or one part of hydrogen atoms may be substituted by the C1-C6 alkyl group of the said amino group; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms; Provided that all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group). The method of claim 1,
(E) The coloring composition whose hardening | curing agent is at least 1 sort (s) chosen from the group which consists of a compound represented by said Formula (1) and Formula (2). delete The coloring pattern formed from the coloring composition of Claim 1 or 2. The color filter provided with the coloring pattern of Claim 4. (1) Process of forming the coating film of the coloring composition of Claim 1 or 2 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 coating film in which the said coloring pattern was formed at 200 degrees C or less. The color display element provided with the color filter of Claim 5.