TW201922962A - Black colored composition and black colored resist composition containing the same wherein the black colored composition is excellent in dispersing capability, high in insulating property, low in dielectric constant, excellent in NMP resistance and high in optical density - Google Patents

Abstract

An object of the present invention is to provide a novel black colored composition, which is excellent in dispersing capability, high in insulating property, low in dielectric constant, excellent in NMP resistance and high in optical density, and a black colored resist composition containing the same. Specifically, the black colored composition is provided to serve as (A) a coloring agent, which contains any one of the following combinations of 1 to 6: 1.a.SV49; 2.a.SV49 and b. blue and/or green pigment; 3.a.SV49, b. blue and/or green pigment and c. purple pigment; 4.a.SV49, b. blue and/or green pigment and e. red and/or orange pigment; 5.b1.PB60 and/or PB80, d. purple coloring agent and e. red and/or orange pigment; 6.e1. at least one selected from the group consisting of PO34, PO72, PR57:1, PR149, PR170, PR179 and PR214, b. blue and/or green pigment and d. purple coloring agent.

Description

Black coloring composition and black colored resist composition containing the same

The present invention relates to a novel black coloring composition and a black colored resist composition comprising the same, which are used for a liquid crystal display element (black matrix of a liquid crystal panel, coloring pitch, formation of a light shielding portion of an organic EL display device), solid-state imaging Infrared transmission (IR-Pass) dispersion used for components (image sensor (image sensor) represented by CCD or CMOS), infrared sensor, etc., excellent dispersibility, high insulation, and dielectric constant Low, NMP resistance, and high optical density.

There are color coincident or uncolored portions near the ends of the red, green, and blue pixels disposed on the color filter of the liquid crystal display element, and when the light passes through the portion, an image projected on the display occurs. The phenomenon of poor contrast or bleeding. Therefore, in order to prevent such a situation from occurring, a black matrix which prevents light transmission can be formed in the vicinity of the end portion of the above-mentioned pixel. Further, studies on forming a black matrix using a black composition obtained by blending a plurality of black colorants and resins have been conventionally performed.
Since the basic function of the black matrix is to prevent transmission of light, carbon black is particularly used as a black coloring agent having a good light-shielding effect, and a pigment dispersant, an alkali-soluble resin, a photopolymerizable compound, and photopolymerization are also used. A resist composition for a black matrix of an initiator or an organic solvent (for example, refer to Patent Document 1 and Patent Document 2).
Further, in the formation of the black matrix, there are a method of simultaneously forming red, green, and blue pixel patterns on the color filter side and a method of forming on the TFT (thin film transistor) array substrate side, and the latter can improve each The advantage of the aperture ratio of the pixel pattern.
However, when the black matrix is disposed on the side of the TFT array substrate, since the black matrix is directly in contact with the pixel electrode and the TFT, the black matrix is required to have high insulation and low dielectric constant.
As a result, in the resist composition for a black matrix in which the conductive carbon black is directly used, a film having high insulating properties and a low dielectric constant cannot be formed. Therefore, in order to solve this problem, the present applicant has proposed a technique in which carbon black after coating a surface by an insulating material carbodiimide compound is used as a resist composition for a black matrix (for example, refer to Patent Document 3) Patent Document 4). By this method, although the insulation of the black matrix is improved to some extent, it is difficult to achieve a higher insulation type which is further demanded by the market only by the system using carbon black.

On the other hand, a black matrix using a plurality of organic pigments and carbon black has been proposed (for example, refer to Patent Document 5). However, the proposed black matrix has a problem that NMP resistance is insufficient.
In addition, the organic pigment has high insulation and a black hue (suspected blackening) can be obtained by mixing the colors. In view of this property, a resist composition for a black matrix having a suspected blackish hue composed of an organic pigment, a pigment dispersant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, or an organic solvent has been proposed (for example, reference) Patent Document 6 and Patent Document 7). However, when a plurality of organic pigments are used, it is sometimes difficult to obtain good dispersibility due to the difference in surface characteristics of the pigment.
Therefore, it has been proposed to use a resist for a black matrix which is composed of an organic pigment, a pigment dispersant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and an organic solvent which are excellent in dispersibility, and which is suspected to be a blackish hue. (for example, refer to Patent Document 8). However, higher optical concentrations and NMP resistance have gradually become a demand in recent years.
[Prior Art Literature]
[Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

An object of the present invention is to provide a novel black colored composition which is excellent in dispersibility, high in insulating property, low in dielectric constant, excellent in NMP resistance, and high in optical density, and a black colored resist composition containing the same.

As a result of intensive studies, the inventors have found that the following 1 to 6 are dispersed as the A. coloring agent by using a dispersing agent and a specific dispersing aid, and it is further preferred to use a dispersing agent and a specific dispersing aid to make carbon black-containing. Since the coloring agent is dispersed and good dispersibility is obtained, the above problems can be all solved, and the present invention has been completed. A. The coloring agent is:
1.a.SV49,
2.a.SV49 and b. blue and/or green pigments,
3.a.SV49, b. blue and / or green pigment and c. purple pigment,
4.a.SV49, b. blue and / or green pigment and e. red and / or orange pigment,
5.b1.PB60 and / or PB80, d. purple colorant and e. red and / or orange pigment,
6. e1. at least one selected from the group consisting of PO34, PO72, PR57:1, PR149, PR170, PR179, and PR214, b. blue and/or green pigment, and d. purple colorant.

That is, the present invention is as follows:
A black coloring composition, wherein the A. coloring agent contains any one of the following combinations of 1 to 6:
1.a.SV49,
2.a.SV49 and b. blue and/or green pigments,
3.a.SV49, b. blue and / or green pigment and c. purple pigment,
4.a.SV49, b. blue and / or green pigment and e. red and / or orange pigment,
5.b1.PB60 and / or PB80, d. purple colorant and e. red and / or orange pigment,
6. e1. at least one selected from the group consisting of PO34, PO72, PR57:1, PR149, PR170, PR179, and PR214, b. blue and/or green pigment, and d. purple colorant.

(2) The black coloring composition according to (1), wherein A. the coloring agent is as follows:
b. The blue and/or green pigment is at least one selected from the group consisting of PB15:3, PB15:4, PB15:6, PB16, PB60, PB75, PB79, PB80, and PG54.
Or c. purple pigment is PV23 and / or PV29,
Or d. The purple colorant is at least one selected from the group consisting of PV23, PV29, and SV49.
Or e. The red and/or orange pigment is selected from the group consisting of PO34, PO38, PO43, PO64, PO69, PO71, PO72, PO73, PR57:1, PR122, PR149, PR166, PR170, PR177, PR179, PR214, PR224, PR242, At least one of PR254, PR264, and PR274.

(3) The black coloring composition according to (1), wherein A. the coloring agent is as follows:
SV49 and b. blue and/or green pigment: at least one selected from the group consisting of PB15:3, PB15:4, PB15:6, PB16, PB60, PB80 and PG54,
Or a.SV49, b. blue and/or green pigment: at least one selected from the group consisting of PB15:3, PB15:4, PB15:6, PB16, PB60, PB80 and PG54 and c. purple pigment: PV23 and/or PV29,
Or a.SV49, b. blue and/or green pigment: at least one selected from the group consisting of PB15:3, PB15:4, PB15:6, PB16, PB60, PB80 and PG54 and e. red and/or orange pigment: At least one selected from the group consisting of PO34, PO38, PO43, PO64, PO69, PO71, PO72, PO73, PR57:1, PR122, PR149, PR166, PR170, PR177, PR179, PR214, PR224, PR242, PR254, PR264, and PR274,
Or e1.PO34, PO72, b. Blue and/or green pigment: at least one selected from the group consisting of PG15, PG16, PB60, PB80 and PG54 and d. Purple colorant: PV23, PV29 and/or SV49.

(4) The black colored composition according to any one of (1) to (3), wherein the A. coloring agent contains carbon black and/or indoleamine black.

(5) The black coloring composition according to any one of (1) to (4) which contains:
B. Dispersing aid with sulfonic acid group
C. Dispersant
D. Adhesive resin
E. Organic solvent.

(6) The black coloring composition according to any one of (1) to (5) which contains an F. polyfunctional epoxy compound.

(7) The black coloring composition according to (5), wherein the dispersing aid having a sulfonic acid group is a dispersing aid and/or a pigment represented by the following general formula (1) and/or (2) Yellow 138 sulfonate,

Wherein X and Y are the same or different and represent a phenyl group which may be substituted by F, C1, Br, NO ₂ , CH ₃ or OCH ₃ , and M represents H, Na, K, NH ₄ or NR1R2R3R4, wherein R1, R2 R3 and R4 are the same or different and each represents a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by another substituent or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted by another substituent, and m represents 1 The above integer.

(8) The black coloring composition according to (6), wherein X of the dispersing aid represented by the formula (1) and/or (2) is 2,5-dichlorophenyl group, and Y is a phenyl group.

(9) The black coloring composition according to (5), wherein the C. dispersing agent is a basic group-containing acrylic resin-based dispersing agent.

(10) The black coloring composition according to (6), wherein the F. polyfunctional epoxy compound has a diphenylmethane skeleton, a dinaphthylene skeleton, a triazine skeleton, a novolac skeleton, a tetraphenylethane skeleton, and a double A polyfunctional epoxy compound having at least one of a phenol skeleton and a biphenyl skeleton.

(11) The black colored composition according to (5), wherein the D. binder resin contains an alkali-soluble resin.

(12) A black colored resist composition containing the black colored composition, the alkali-soluble resin, the photopolymerizable compound, and the photopolymerization initiator according to any one of (1) to (11).

According to the present invention, by forming a black coloring composition containing a specific organic pigment and a black coloring resist composition, it is excellent in dispersibility, high in insulation, low in dielectric constant, good in NMP resistance, optical density, and infrared light transmission. The rate is high, the light-shielding property is also excellent, and the fluidity and dispersion stability are excellent.

The black coloring composition of the present invention (hereinafter also simply referred to as "coloring composition") will be described in further detail.
The coloring composition of the present invention is based on any one of the following 1 to 6 as a coloring agent:
1.a.SV49,
2.a.SV49 and b. blue and/or green pigments,
3.a.SV49, b. blue and / or green pigment and c. purple pigment,
4.a.SV49, b. blue and / or green pigment and e. red and / or orange pigment,
5.b1.PB60 and / or PB80, d. purple colorant and e. red and / or orange pigment,
6. e1. at least one selected from the group consisting of PO34, PO72, PR57:1, PR149, PR170, PR179, and PR214, b. blue and/or green pigment, and d. violet colorant. Hereinafter, constituent materials typified by these coloring agents will be described.

[A. Colorant]
In the present invention, as the A. coloring agent, a coloring agent based on any one of the following 1 to 6 is used:
1.a.SV49,
2.a.SV49 and b. blue and/or green pigments,
3.a.SV49, b. blue and / or green pigment and c. purple pigment,
4.a.SV49, b. blue and / or green pigment and e. red and / or orange pigment,
5.b1.PB60 and / or PB80, d. purple colorant and e. red and / or orange pigment,
6. e1. at least one selected from the group consisting of PO34, PO72, PR57:1, PR149, PR170, PR179, and PR214, b. blue and/or green pigment, and d. purple colorant.

Further, from the viewpoint of heat resistance, optical density, and balance of NMP resistance of the coloring composition and the black colored resist composition, it is preferable to use a coloring agent containing the following as the A. coloring agent:
b. Blue and/or green pigment: at least one selected from the group consisting of PB15:3, PB15:4, PB15:6, PB16, PB60, PB75, PB79, PB80 and PG54,
Or c. purple pigment: PV23 and / or PV29,
Or d. purple colorant: at least one selected from the group consisting of PV23, PV29 and SV49,
Or e. Red and/or orange pigments: PO34, PO38, PO43, PO64, PO69, PO71, PO72, PO73, PR57:1, PR122, PR149, PR166, PR170, PR177, PR179, PR214, PR224, PR242, PR254.

Further, from the viewpoint of NMP resistance, it is preferred to use a coloring agent containing the following substances:
SV49 and b. blue and/or green pigment: at least one selected from the group consisting of PB15:3, PB15:4, PB15:6, PB16, PB60, PB80 and PG54,
Or a.SV49 and b. Blue and/or green pigment: at least one selected from the group consisting of PB15:3, PB15:4, PB15:6, PB16, PB60, PB80 and PG54, c. Purple pigment: PV23 and/or PV29,
Or a.SV49, b. blue and/or green pigment: at least one selected from the group consisting of PB15:3, PB15:4, PB15:6, PB16, PB60, PB80 and PG54 and e. red and/or orange pigment: At least one selected from the group consisting of PO34, PO38, PO43, PO64, PO69, PO71, PO72, PO73, PR57:1, PR122, PR149, PR166, PR170, PR177, PR179, PR214, PR224, PR242, PR254, PR264, and PR274,
Or e1.PO34, PO72, b. Blue and/or green pigment: at least one selected from the group consisting of PG15, PG16, PB60, PB80 and PG54 and d. Purple colorant: PV23, PV29 and/or SV49.

When carbon black or indole amine black is not used, the preferred compounding ratio is as follows:
The mixing ratio of SV49 and b. blue and/or green pigment is a: b=90~30:10~70,
The mixing ratio of SV49, b. blue and/or green pigment and c. purple pigment is a: b: c = 15~50: 20~60: 10~40,
The blending ratio of SV49, b. blue and/or green pigment and e. red and/or orange pigment is a: b: e = 10~80: 5~60: 5~60,
B1. PB60 and / or PB80 and d. purple colorant and e. red and / or orange pigment blend ratio b1: d: e = 10 ~ 70: 10 ~ 60: 10 ~ 60,
E1. a compounding ratio of at least one selected from the group consisting of PO34, PO72, PR57:1, PR149, PR170, PR179, and/or PR214, b. blue and/or green pigment, and d. purple colorant: e1:b:d =10~60:10~70:10~60.
When a higher optical density is further required, it is preferred to use carbon black and/or indoleamine black as a colorant. A good optical density can be obtained by being a coloring component of the present invention.

(carbon black)
As the carbon black constituting the black colored composition of the present invention, it is preferred to use neutral carbon black having an average primary particle diameter of 20 to 60 nm and/or acidic carbon black having an average primary particle diameter of 20 to 60 nm.
The neutral carbon black preferably has a pH of more than 9, and specifically, Printex 25 (average primary particle diameter: 56 nm, pH 9.5) manufactured by Degussa Co., Ltd., Printex 35 (average primary particle diameter: 31 nm, pH 9.5), Printex 65 (average primary particle diameter: 21 nm, pH 9.5), MA#20 (average primary particle diameter: 40 nm, pH 8.0) manufactured by Mitsubishi Chemical Corporation, MA#40 (average primary particle diameter: 40 nm, pH 8.0), MA#30 (average primary particle diameter: 30 nm, pH 8.0) and the like.
The acidic carbon black preferably has a pH in the range of 2 to 4. Specifically, Raven 1080 (average primary particle diameter: 28 nm, pH 2.4) and Raven 1100 (average primary particle diameter: 32 nm, pH 2.) manufactured by Columbia Chemicals Co., Ltd. are mentioned. 9), MA-8 (average primary particle size: 24 nm, pH 3.0), MA-100 (average primary particle size: 22 nm, pH 3.5) manufactured by Mitsubishi Chemical Corporation, and SPECIAL BLACK 250 manufactured by Degussa Co., Ltd. (on average The particle diameter was 56 nm, pH 3.0), SPECIAL BLACK 350 (average primary particle diameter: 31 nm, pH 3.0), and SPECIAL BLACK 550 (average primary particle diameter: 25 nm, pH 4).
The pH can be determined by adding 1 g of carbon black into 20 ml of distilled water (pH 7.0), mixed with a magnetic stirrer, and prepared into an aqueous suspension, and measured at 25 ° C using a glass electrode (German Industrial Standard) Specifications DIN ISO 787/9).
The average primary particle diameter is a value of an arithmetic mean diameter observed by an electron microscope.
Further, the pH and the average primary particle diameter of the above carbon black are values of product catalogs.
When carbon black is used in combination, it is preferable to blend the coloring agent into 30% by mass or less.

(indoleamine black)
As the indoleamine black, a known indoleamine black having the following structure can be used. Specifically, Irgaphor Black S 0100 CF (manufactured by BASF Corporation) or the like can be mentioned. When indoleamine black is used, it is preferably blended in a coloring agent to be 50% by mass or less.

Further, in the black colored composition, the total amount of carbon black and indoleamine black is preferably 60% by mass or less.

(other colorants)
Other coloring agents such as the above component A and yellow pigment may be used in combination within a range not impairing the effects of the present invention. As such a coloring agent, a well-known coloring agent used conventionally can be used.
PY 83, 110, 128, 138, 139, 150, 151, 154, 155, 180, 181, etc. are mentioned as a preferable yellow pigment.

In the present invention, as the "black coloring composition", for example, when a black colored resist composition to be described later is prepared, the black colored resist composition is a film of 1 μm by a spin coater. The black colored resist pattern formed only on the solid portion was measured by using a Macbeth densitometer (TD-931, manufactured by Macbeth Co., Ltd.) on a glass substrate. The optical density (OD value) is required to be 0.6 or more, more preferably 1.2 or more, still more preferably 1.4 or more.

[B. Dispersing Aid with Sulfonic Acid Group]
In the black coloring composition of the present invention, the above B. dispersing aid having a sulfonic acid group can be used for dispersing the above coloring agent.
The dispersing aid having a sulfonic acid group in the present invention may, for example, be a compound represented by the following formula (1) and/or (2), a sulfonate of the pigment yellow 138, a sulfonate having a phthalocyanine skeleton, or the like. a sulfonate of a fluorene skeleton, a sulfonate having a naphthalene skeleton, and the like.
In the dispersing aid having a sulfonic acid group in the present invention, a compound represented by the following formula (1) and/or (2) and/or a sulfonate of the pigment yellow 138 are preferably used. When the coloring agent is dispersed, by using the dispersing aid having a sulfonic acid group and a dispersing agent containing a basic group, excellent fluidity and dispersion stability can be obtained in the black colored composition. Further, when the black colored composition is used as a black colored resist composition, a high optical density can be obtained.

The compound represented by the above formula (1) and/or (2) will be described.
In the above formulae (1) and (2), X and Y are the same or different and each represents a phenyl group which may be substituted by F, C1, Br, NO ₂ , CH ₃ or OCH ₃ . M represents H, Na, K, NH ₄ or NR1R2R3R4.
With respect to "NR1R2R3R4" (M) of the above formulas (1) and (2), R1, R2, R3 and R4 are the same or different, and represent a saturated or unsaturated aliphatic group having 1 to 10 carbon atoms which may be substituted by another substituent. A hydrocarbon group or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted by another substituent. Here, examples of the saturated or unsaturated aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a pentyl group, and a hexyl group. An alkyl group such as an octyl group or a fluorenyl group; an alkenyl group such as a vinyl group, an allyl group or a 1-butenyl group; an alkynyl group such as an ethynyl group or a propynyl group; and the like. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Further, examples of the other substituent include a hydroxyl group, a halogen group, a carboxyl group, an amino group, and a lower alkyl group (having 1 to 5 carbon atoms).
Further, one of the above R1R2R3 and R4 may be substituted with another substituent, or two or more of them may be substituted with another substituent.
Further, "m" of the above formulas (1) and (2) is an integer of 1 or more.

In the above-mentioned compound (dispersing aid), the compound represented by the above formula (1) is an enol type, and the compound represented by the above formula (2) is a keto type tautomer, and the dispersing aid includes These two compounds. In other words, the dispersing aid includes any of the compounds represented by the above formula (1) or (2) and the compounds represented by the above formulas (1) and (2). One.
Such a dispersing aid is a novel compound, and can be produced, for example, by dissolving a monoazo compound of the following formulas (3) to (30) in concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or a mixture thereof. The mixture was heated to room temperature or even 80 to 90 ° C, and then diluted with a large amount of water, and the obtained suspension was filtered, washed with water, and the obtained cake was dried and pulverized, and no commercially available product was present.

Among these dispersing assistants having a sulfonic acid group, the above formula (1) and/or are considered from the viewpoint of having a good optical fluidity and dispersion stability while obtaining a black color resist composition having a higher optical density. (2) A compound represented by the following formula (31) wherein X is 2,5-dichlorophenyl and Y is a phenyl group (the monoazo compound of the above formula (3) is obtained by the above production method. The compound: an enol type) and/or a compound represented by the following formula (32) (a compound obtained by the above production method using the monoazo compound of the above formula (4): a ketone type) is particularly suitable.

The total amount of the dispersing aid having a sulfonic acid group in the present invention is usually preferably 30 parts by mass or less, and more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the total coloring agent. When the amount of the dispersing aid having a sulfonic acid group is more than the above range, the dispersion effect does not necessarily increase.
Further, as the dispersing aid having a sulfonic acid group for dispersing the organic pigment, in addition to the dispersing aid having a sulfonic acid group described above, other dispersing aids may be used in combination.

[C. Dispersant]
As the C. dispersing agent in the present invention, an anionic surfactant, a basic group-containing polyester-based dispersing agent, a basic group-containing acrylic resin-based dispersing agent, and a basic group-containing carbamate can be used. An ester resin dispersant, a basic group-containing carbodiimide resin dispersant, and the like.
These dispersing agents may be used singly or in combination of two or more kinds. Among them, from the viewpoint of obtaining good dispersibility, it is preferred to use a basic group-containing polyester-based dispersant, a basic group-containing acrylic resin dispersant, and a basic group-containing urethane-based resin dispersant. A carbodiimide-based resin dispersant containing a basic group.

As the polymer dispersing agent having a basic group, for example, the following compounds can be mentioned:
(1) Amino group and/or imino group of a polyamine compound (for example, a poly(lower) alkyleneamine such as polyallylamine, polyvinylamine or polyethyleneimine) and a polyester selected from the group consisting of a polyester having a free carboxyl group A reaction product of at least one of polyamine and polyester decylamine.
(2) A carbodiimide compound having at least one side chain selected from the group consisting of a polyester side chain, a polyether side chain, and a polypropylene side chain, and a basic nitrogen-containing group in the molecule.
(3) A reaction product of a low molecular weight ammonia compound such as poly(lower) alkyleneimine or methyliminobispropylamine and a polyester having a free carboxyl group.
(4) The isocyanate group of the polyisocyanate compound is a polyester having one hydroxyl group such as an alcohol such as methoxypolyethylene glycol or a caprolactone polyester, and has 2 to 3 isocyanate-reactive functional groups. A reaction product obtained by reacting a compound, an aliphatic or heterocyclic hydrocarbon compound having an isocyanate-reactive functional group and a tertiary amino group.
(5) A reaction product of reacting a polymer of an acrylate having an alcoholic hydroxyl group with a polyisocyanate compound and a hydrocarbon compound having an amino group.
(6) A reaction product obtained by adding a low molecular weight ammonia compound to a polyether chain.
(7) A reaction product obtained by reacting a compound having an isocyanate group with a compound having an amino group.
(8) A reaction product obtained by reacting a polyepoxy compound with a linear polymer having a free carboxyl group and an organic amine compound having one secondary amino group.
(9) A reaction product of a polycarbonate compound having a functional group reactive with an amino group at one end and a polyamine compound.
(10) selected from the group consisting of methyl methacrylate, methyl methacrylate, methyl propyl acrylate, methyl butyl acrylate, methyl stearyl acrylate, methyl benzyl acrylate, methacrylate, ethacrylic acid At least one of methyl acrylate or acrylate such as ester, propyl acrylate, butyl acrylate, stearyl acrylate or benzyl acrylate, and acrylamide, methacrylamide, N-hydroxyl At least one of a basic group-containing polymerizable monomer such as a base amine, a vinyl imidazole, a vinyl pyridine, a monomer having an amino group and a polycaprolactone skeleton, and a styrene, a styrene derivative, or the like A copolymer of at least one of the polymerizable monomers.
(11) An acrylic block copolymer composed of a block having a basic group such as a tertiary amino group or a quaternary ammonium base and a block having no basic functional group.
(12) A dispersant obtained by subjecting a polyallylamine to a polycarbonate compound by a Michael addition reaction.
(13) A carbodiimide compound having at least one polybutadiene chain and a basic nitrogen-containing group, respectively.
(14) A carbodiimide compound having at least one side chain having a guanamine group and a basic nitrogen-containing group in the molecule.
(15) A polyurethane-based compound or an acrylic compound having a constituent unit containing an ethylene oxide chain and a propylene oxide chain and having an amino group which is quaternized by a quaternary ammonating agent.
(16) a compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in a molecule with an active hydrogen group of a compound having an active hydrogen group and having a carbazole ring and/or an azobenzene skeleton in the molecule. The carbazole ring and the total amount of the urethane bond and the urea bond formed by reacting the isocyanate group with the active hydrogen group in the molecule relative to the isocyanate group of the isocyanate compound having an isocyanurate ring. The number of azobenzene skeletons is 15 to 85% and the like.

Among these basic group-containing polymer dispersants, a basic group-containing urethane polymer dispersant, a basic group-containing polyester polymer dispersant, and a basic group are more preferable. The acrylic polymer dispersant is more preferably an amino group-containing urethane polymer dispersant, an amino group-containing polyester polymer dispersant, or an amino group-containing acrylic polymer dispersant. An acrylic polymer-containing dispersing agent containing a basic group is particularly preferable.
The amount of the dispersing agent containing a basic group is preferably 1 to 200 parts by mass, more preferably 1 to 60 parts by mass, per 100 parts by mass of the component A.

[D. Binder resin]
In the black coloring composition, the D. binder resin may, for example, be a thermosetting resin, a thermoplastic resin, an alkali-soluble resin or a photopolymerizable compound (photopolymerizable resin) having one or more photopolymerizations in the molecule. Monomers, oligomers, etc. of unsaturated bonds, etc.). These can be used individually or in combination of 2 or more types.
Among them, an alkali-soluble resin is preferably used from the viewpoint of performing alkali developability by development with an alkaline solution.
Such a binder resin is represented by a mass fraction with respect to the total solid content of the black coloring composition, and is preferably from 0.5 to 94% by mass, and more preferably from 0.5 to 50% by mass, based on the total amount of the binder resin to be used. The scope.
Examples of the thermosetting resin and the thermoplastic resin include a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, and the like. Polyvinyl acetate, urethane resin, phenolic resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, cellulose, poly Butadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin, and the like.
As the alkali-soluble resin, for example, a carboxyl group-containing alkali-soluble resin is preferred: acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, monoalkyl maleate, citraconic acid, citraconic anhydride a carboxyl group-containing unsaturated monomer such as citraconate monoalkyl ester and selected from the group consisting of styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, Benzyl acrylate, methyl benzyl acrylate, glyceryl monoacrylate, methyl glyceryl acrylate, mono(meth) acrylate having a dicyclopentadiene skeleton, a tricyclopropane cyclohexane ring, N-benzene A copolymer obtained by reacting at least one of a kiylimine, a polystyrene macromonomer, and a polymethyl methacrylate macromonomer.
Among them, from the viewpoint of improving heat resistance, an alkali-soluble acrylic resin capable of obtaining high heat resistance is preferable.
The alkali-soluble resin preferably has an acid value of 10 to 300 mgKOH/g, a weight average molecular weight of 1,000 to 200,000, more preferably an acid value of 20 to 200 mgKOH/g, and a weight average molecular weight of 3,000~ from the viewpoint of film formability and alkali developability. 100,000.
The alkali-soluble resin may be used singly or in combination of two or more kinds depending on the function required. The weight average molecular weight is a weight average molecular weight in terms of polystyrene, and is measured in the same manner as the acid group-containing resin.

The photopolymerizable resin of the photopolymerizable compound can be introduced into a photocrosslinkable group such as a (meth)acrylic acid compound or cinnamic acid via an isocyanate group, an aldehyde group or an epoxy group to have a hydroxyl group, a carboxyl group or an amino group. A resin of a linear polymer such as a reactive substituent. A (meth) group having a hydroxyl group such as a hydroxyalkyl (meth) acrylate such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer, which is an acid anhydride-containing linear polymer. A polymer in which an acrylic compound is subjected to a half esterification.
Examples of the monomer having one photopolymerizable unsaturated bond in the molecule of the photopolymerizable compound include methyl methacrylate, methyl butyl acrylate, methyl 2-ethylhexyl acrylate, and methacrylate. Methyl methacrylate or acrylate such as butyl acrylate or 2-ethylhexyl acrylate; methyl aralkyl acrylate or acrylate such as methyl benzyl acrylate or benzyl acrylate; butoxyethyl Methyl alkoxyalkyl acrylate or acrylate such as methyl acrylate or butoxyethyl acrylate; N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl acrylate a methyl methacrylate or an acrylate such as an ester; or a polyalkylene glycol alkyl ether such as diethylene glycol ethyl ether, triethylene glycol butyl ether or dipropylene glycol methyl ether; Acrylate; methyl acrylate or acrylate of polyalkylene glycol aryl ether such as hexaethylene glycol phenyl ether; isobornyl methacrylate or acrylate; methyl glyceryl acrylate or acrylate; Methyl hydroxyethyl acrylate or acrylate.
Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule of the photopolymerizable compound include bisphenol A methyl diacrylate, 1,4-butanediol diacrylate methyl ester, and 1,3-butylene. Methyl diol diacrylate, methyl diethylene glycol diacrylate, methyl glyceryl diacrylate, methyl neopentyl glycol diacrylate, methyl polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethyl Methyl diol diacrylate, methyl trimethylolpropane triacrylate, methyl pentaerythritol triacrylate, methyl pentaerythritol tetramethyl acrylate, methyl dipentaerythritol tetraacrylate, methyl dipentaerythritol hexaacrylate, methyl dipentaerythritol penta acrylate, Bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glyceryl diacrylate, neopentyl glycol diacrylate , polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate , dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like.

[E. Organic solvents]
The organic solvent used in the black coloring composition of the present invention is such that the coloring agent conventionally used can be stably dispersed, and the above-mentioned B. dispersing aid having a sulfonic acid group, C. dispersing agent, and D. binder can be used. resin dissolved organic solvent, preferably under atmospheric pressure (1.013 × 10 ² kPa) based organic solvent having a boiling point of 100 ~ 250 ℃, the ether-based organic solvents, ether ester organic solvents, ketone organic solvents, aromatic hydrocarbon-based organic A solvent, a nitrogen-containing organic solvent, or the like.
Specific examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethyl An ether organic solvent such as diol methyl ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl An ether ester organic solvent such as a vinyl ether acetate or a propylene glycol monoethyl ether acetate; a ketone organic solvent such as methyl isobutyl ketone, cyclohexanone, 2-heptanone or δ-butyrolactone; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, formic acid-n - ester organic solvents such as amyl ester; methanol, ethanol, isopropyl alcohol, butyl And the like alcohol solvents; N-methylpyrrolidone, N, N- dimethylformamide, N, N- dimethylacetamide and the like of the nitrogen-containing organic solvent. These may be used alone or in combination of two or more.

[F. Polyfunctional epoxy compound]
The black coloring composition of the present invention preferably contains a polyfunctional epoxy compound.
When acidic carbon black is used, since the polyfunctional epoxy compound interacts well with the functional group present on the surface of the acidic carbon black, high insulation can be imparted.
Further, the black colored resist composition using the black colored composition of the present invention can effectively function when a thermosetting pattern is formed.
As the polyfunctional epoxy compound, a polyfunctional epoxy compound conventionally used for forming a black colored composition can be mentioned.
The polyfunctional epoxy compound may, for example, be selected from the group consisting of a diphenylmethane skeleton, a dinaphthylene skeleton, a triazine skeleton, a biphenyl skeleton, a phenolic novolac skeleton, a tetraphenylethane skeleton, and a bisphenol skeleton. At least one backbone of a multifunctional epoxy compound.
Among the above polyfunctional epoxy compounds, a polyfunctional epoxy compound having at least one skeleton selected from the group consisting of a diphenylmethane skeleton, a dinaphthylene skeleton, a triazine skeleton, and a biphenyl skeleton is preferable.
As the polyfunctional epoxy compound having at least one skeleton selected from the above-mentioned diphenylmethane skeleton, dinaphthylene skeleton, triazine skeleton, and biphenyl skeleton, it is exemplified:

Product name: TEPIC (manufactured by Nissan Chemical Co., Ltd.),

Product name: EPICLON830 (made by DIC company),

Product name: JER-YX-4000 (manufactured by Mitsubishi Chemical Corporation),

Product name: JER-604 (manufactured by Mitsubishi Chemical Corporation). Among the above polyfunctional epoxy compounds, a tetrafunctional or higher polyfunctional epoxy compound is preferred. It is considered that as long as it is a tetrafunctional or higher polyfunctional epoxy compound, it is excellent in film maintenance property at a high temperature, and it is possible to maintain bulkiness while ensuring high insulation. The tetrafunctional or higher polyfunctional epoxy compound is more preferably a tetrafunctional or higher polyfunctional epoxy compound having a diphenylmethane skeleton, a dinaphthylene skeleton, a triazine skeleton, and a biphenyl skeleton. As such a compound, a product name: JER-604 (manufactured by Mitsubishi Chemical Corporation) can be cited.
The polyfunctional epoxy compound is contained in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the total colorant. When the content of the polyfunctional epoxy compound is less than 0.1 part by mass, problems such as a black coloring composition which does not provide high resistance may occur, and when the content of the polyfunctional epoxy compound is more than 20 parts by mass, The stability of the dispersion may be destroyed due to the polymerization of the epoxy group.
The black coloring composition of the present invention is preferably mainly composed of the above-mentioned A to F components, and these components usually account for 90 to 100% by mass in the black coloring composition.

(Additives that can be added as needed)
Various additives such as a photopolymerization initiator, a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant, and a photopolymerizable compound can be suitably used according to the manufacturing method of a black coloring composition. As the photopolymerization initiator, for example, a photopolymerization initiator to be described later can be mentioned.

[Manufacturing method of black coloring composition]
An example of a method of producing a colored composition using the above materials will be described.
As a dispersion treatment method, for example, when a colored component containing no carbon black or indoleamine black is dispersed, a mixture of any one of the above combinations 1 to 6 and a mixture containing B to F is used. A method of performing dispersion treatment, such as a machine, a kneader, a high-speed mixer, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, a high-pressure dispersing device, and the like.
When carbon black or indoleamine black is used as the A. coloring agent, the following method can be exemplified: (1) A. Any one of the above combinations of 1 to 6, a coloring agent, carbon black, and/or indole amine black and B The mixture of the ~F component is subjected to a dispersion treatment using a roll mill, a kneader, a high speed mixer, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, a high pressure dispersing device, etc., (2) A. The above 1~ a combination of any one of the combinations of the coloring agent, the intrinsic amine black, and the mixture containing the B to F components, using a roll mill, a kneader, a high speed mixer, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, Dispersing treatment of a high-pressure dispersing device or the like, and dispersing the obtained mixture and carbon black using a roll mill, a kneader, a high-speed stirrer, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, a high-pressure dispersing device, or the like (3) A. Any one of the above combinations of 1 to 6 and a mixture containing a B to F component, a mixture of carbon black and a component comprising B to E, and/or an indole amine black and a component comprising B to E The mixture is separately dispersed and will be obtained A method in which each dispersion is subjected to a mixing treatment or the like.
Further, the F component may be added after the dispersion treatment to carry out a mixing treatment.
When carbon black is used as the A. coloring agent and the component A and the carbon black are co-dispersed, since carbon black tends to be excessively dispersed, it is preferred to separately disperse the coloring agent of A.1 to 6 and the carbon black.

Next, an example of a black colored resist composition (hereinafter also simply referred to as "resist composition") in which the black colored composition of the present invention is used for photolithography will be described.
The black coloring resist composition is mainly composed of a coloring agent, a dispersing agent, a sulfonic acid group-containing dispersing aid, a binder resin, a photopolymerization initiator, and an organic solvent, and examples of the binder resin include a base. A binder resin of a soluble resin and a photopolymerizable compound.

<Constituent material of black coloring resist composition>
(Colorant)
As the coloring agent, the same substance as described in the above black colored composition was used.
The amount of the coloring agent used is expressed by mass fraction with respect to the total solid content of the black colored resist composition, and is preferably 20 to 90% by mass, and more preferably 30 to 60% by mass based on the total amount of the coloring agent used.

(Dispersing aid containing sulfonic acid groups)
As the dispersing aid containing a sulfonic acid group, the same substance as described in the above black colored composition is used.
In the black coloring resist composition, the amount of the sulfonic acid group-containing dispersing aid to be used is usually preferably 30 parts by mass or less, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of all the coloring agents used. . There is a tendency that the dispersion effect does not increase even if the amount of the sulfonic acid group-containing dispersing aid used exceeds the above range.

(Dispersant)
As the dispersing agent, the same substance as described in the above black colored composition was used.
In the black coloring resist composition, the amount of the dispersing agent used is usually preferably from 1 to 200 parts by mass, more preferably from 1 to 60 parts by mass, per 100 parts by mass of all the coloring agents used. When the amount of the dispersant used is less than 1 part by mass, the dispersibility may be deteriorated. On the other hand, when it exceeds 200 mass parts with respect to 100 mass parts of all the coloring agents used, the developability may worsen.

(alkali soluble resin as binder resin)
As the alkali-soluble resin, the same substance as described in the above black colored composition is used.
In the black coloring resist composition, the amount of the alkali-soluble resin to be used is usually preferably 10 to 1,000 parts by mass, more preferably 10 to 500 parts by mass, based on 100 parts by mass of all the coloring agents used. In this case, when the amount of the alkali-soluble resin used is less than 10 parts by mass, for example, there is a possibility that the alkali developability is deteriorated or scum is formed on the substrate of the unexposed portion or the light-shielding layer, and the film remains. On the other hand, when it exceeds 1,000 parts by mass, the concentration of the colorant may be relatively lowered, so that it is difficult to achieve the target optical density when the film is formed.

(Photopolymerizable compound as a binder resin)
The photopolymerizable compound is a monomer or oligomer having one or more photopolymerizable unsaturated bonds in the molecule, and the same substance as described in the above colored composition is used.
These photopolymerizable compounds may be used singly or in combination of two or more kinds. The amount of use of the photopolymerizable compound is preferably from 3 to 50% by mass based on the total solid content of the black colored resist composition in terms of mass fraction.

(photopolymerization initiator)
The photopolymerization initiator is not particularly limited, and examples thereof include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, and 4-methoxy-4'-dimethyl group. Aminobenzophenone, benzoin, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylbenzene Ketone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl benzophenone, tert-butyl sulfonium, 1-chloropurine, 2,3-dichloropurine, 3-chloro-2-methyl Base, 2-ethyl hydrazine, 1,4-naphthoquinone, 1,2-benzopyrene, 1,4-dimethylhydrazine, 2-phenylhydrazine, 2-methyl-1 [ 4-(methylthio)phenyl]-2-morpholinylpropan-1-one, an oxime ester photopolymerization initiator, a triazine-based photopolymerization initiator, and the like. These photopolymerization initiators may be used alone or in combination of two or more.
The amount of use of the photopolymerization initiator is preferably from 1 to 20% by mass based on the total solid content of the black colored resist composition.

(Organic solvents)
The organic solvent to be used for the black coloring resist is preferably an ester organic solvent, an ether organic solvent, an ether ester organic solvent or a ketone having a boiling point of 100 to 250 ° C at normal pressure (1.013 × 10 ² kPa). An organic solvent, an aromatic hydrocarbon organic solvent, a nitrogen-containing organic solvent, or the like. When a large amount of the organic solvent having a boiling point of more than 250 ° C is contained, when the coating film formed by coating is pre-baked, the organic solvent does not sufficiently evaporate and remains in the dried coating film, and the heat resistance of the dried coating film may be deteriorated. Further, when a large amount of an organic solvent having a boiling point of less than 100 ° C is contained, it is difficult to apply without mottle and uniform, and a coating film excellent in surface smoothness may not be obtained.
Specific examples of the preferred solvent include the same organic solvents as those used in the above black colored composition.
Among these organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, and the like are preferable from the viewpoints of solubility, dispersibility, coatability, and the like. Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutyl propionate Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, etc., more preferably propylene glycol monomethyl ether acetate.
Furthermore, in the black colored resist composition, the content of the organic solvent is preferably 50% by mass or more, and more preferably 70% by mass or more, from the viewpoint of solubility, dispersibility, and coating property of the alkali-soluble resin. .

Examples of the black coloring resist composition include those mainly composed of a coloring agent, a dispersing agent, a sulfonic acid group-containing dispersing aid, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and an organic solvent. The composition usually accounts for 90 to 100% by mass in the black colored resist composition.

(Additives that can be added as needed)
In the black coloring resist composition, various additives such as a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant can be suitably used as needed.

<Method for Producing Black Colored Resist Composition>
An example of a method of producing a black colored resist composition using the above materials is shown.
〔Production method〕
A photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, an organic solvent, and other additives as needed, and a stirring device such as a high-speed agitator are used in the black coloring composition obtained by the method for producing a black coloring resist composition. After uniformly mixing, it was filtered with a filter to obtain a black colored resist composition.
Example

Next, a colored composition for a black matrix according to one embodiment of the present invention and a colored resist composition for a black matrix containing the same will be described.
The present invention is specifically described by the embodiments, and the present invention is not limited to the embodiments as long as they do not depart from the gist of the invention. Further, "parts" and "%" in the present embodiment represent "parts by mass" and "% by mass", respectively, unless otherwise stated.
<colorant>
PV23 (Pigment Violet 23)
PV29 (Pigment Violet 29)
SV49 (solvent violet 49)
PB15 (Pigment Blue 15:3)
PB15 (Pigment Blue 15:4)
PB15 (Pigment Blue 15:6)
PB16 (Pigment Blue 16)
PB60 (Pigment Blue 60)
PB75 (Pigment Blue 75)
PB79 (Pigment Blue 79)
PB80 (Pigment Blue 80)
PG54 (Pigment Green 54)
PG60 (Pigment Green 60)
PO34 (Pigment Orange 34)
PO38 (Pigment Orange 38)
PO43 (Pigment Orange 43)
PO64 (Pigment Orange 64)
PO69 (Pigment Orange 69)
PO71 (Pigment Orange 71)
PO72 (Pigment Orange 72)
PO73 (Pigment Orange 73)
PR57:1 (Pigment Red 57:1)
PR122 (Pigment Red 122)
PR149 (Pigment Red 149)
PR166 (Pigment Red 166)
PR170 (Pigment Red 170)
PR177 (Pigment Red 177)
PR179 (Pigment Red 179)
PR214 (Pigment Red 214)
PR224 (Pigment Red 224)
PR242 (Pigment Red 242)
PR254 (Pigment Red 254)
PR264 (Pigment Red 264)
PR274 (Pigment Red 274)
Carbon black (acidic carbon black)
Indoleamine black (Irgaphor Black S 0100, CF, BASF)
Dark

<Polymer dispersant containing a basic group>
BYK-LPN-22102 (company name: Acrylic block copolymer containing basic group, made by BYK Chemical Co., Ltd.)

<Dispersing aid containing sulfonic acid group>
(Dispersing aid 1)
30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask, and 10 g of Pigment Red 2 (the compound represented by the above formula (3) and/or (4)) was added while stirring with a magnetic stirrer, and the mixture was stirred at room temperature for 30 minutes. A 1 L beaker was charged with a mixture of 50 g of water and 50 g of ice, and the above reactant was poured into the ice water, and stirred with a magnetic stirrer for 30 minutes. This was filtered under reduced pressure, washed with water, and the obtained solid was dried to obtain 12 g of the target substance (the compound represented by the above formula (31) and/or (32): M = H).
(Dispersing Aid 2)
30 ml of concentrated sulfuric acid was placed in a 100 ml Erlenmeyer flask, and 10 g of CI Pigment Yellow 138 was added while stirring with a magnetic stirrer, and the mixture was stirred at room temperature for 30 minutes. A 1 L beaker was charged with a mixture of 50 g of water and 50 g of ice, and the above reactant was poured into the ice water, and stirred with a magnetic stirrer for 30 minutes. This was filtered under reduced pressure, washed with water, and the obtained solid was dried to obtain 12 g of a sulfonate of the target substance Pigment Yellow 138.

<alkali soluble resin>
BMM/MAA copolymer (methyl methacrylate/methacrylic acid copolymer, theoretical acid value: 120 mg KOH/g, weight average molecular weight: 25,000)
<Photopolymerizable compound>
DPEHA (dipentaerythritol hexaacrylate)
<Photopolymerization initiator>
IRGACURE OXE 02(1-[9-ethyl-6-(2-methylbenzomethyl)-9H-indazol-3-yl]-ethanone-1-(O-acetyl))

<organic solvent>
PGMEA (propylene glycol monomethyl ether acetate)
PGME (propylene glycol monomethyl ether)

(Manufacture of coloring composition for black matrix)
The mixture of the compositions described in Tables 1 to 3 was kneaded by a circulating bead mill under the following conditions to obtain colored compositions for black matrices according to Examples A1 to 37 and Comparative Examples A1 to 5. Further, the numerical unit indicating the composition is mass%.
Circulating bead mill: content 150ml
The amount of circulating mixture: 1kg
Distributed load: 100%
Cycle temperature: 50 ° C
Circumferential speed: 9~10m/s
Discharge amount: 200g/min
Cycle time: 2 hours

Table 1

Table 2

table 3

(Manufacture of a colored resist composition for a black matrix)
The black matrix coloring composition and other materials according to the above Examples A1 to 37 and Comparative Examples A1 to 5 were composed of the compositions of Tables 4 to 6, and were uniformly mixed using a high-speed mixer, and then filtered with a filter having a pore size of 3 μm to obtain Examples. A coloring resist composition for the black matrix of B1 to 37 and Comparative Examples B1 to 5.

Table 4

Black matrix coloring resist composition embodiment
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
B13
B14
Coloring Composition Example A1
Example A2
Example A3
Example A4
Example A5
Example A6
Example A7
Example A8
Example A9
Example A10
Example A11
Example A12
Example A13
Example A14
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
Alkali soluble resin
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
DPEHA
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
OXE02
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
PGMEA
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
total
100.0%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
Pigment ratio in solid content
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.00%
35.00%
35.0%
35.0%
Evaluation results

Photosensitive coloring composition initial viscosity (cp)
5
5
5
5
4
4
6
5
6
4
4
4
5
6
40 ° C / 7 days (cp)
6
5
5
5
4
4
6
5
6
4
4
4
5
6
Surface resistance (Ω/□)
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
OD (1μ/m)
1.4
1.4
1.4
1.4
1.4
1.7
1.6
1.6
1.9
1.8
1.7
1.9
1.5
1.5
Solvent resistance (maximum Abs.)
1.2
0.8
0.8
0.8
0.7
0.8
0.9
1.4
1.2
0.7
1.1
0.9
0.8
0.9
Film color hue black black black black black black black black black black black black

table 5

Black matrix coloring resist composition embodiment
B15
B16
B17
B18
B19
B20
B21
B22
B23
B24
B25
B26
B27
B28
Coloring Composition Example A15
Example A16
Example A17
Example A18
Example A19
Example A20
Example A21
Example A22
Example A23
Example A24
Example A25
Example A26
Example A27
Example A28
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
Alkali soluble resin
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
DPEHA
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
OXE02
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
PGMEA
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
total
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
Pigment ratio in solid content
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.00%
35.00%
35.0%
35.0%
Evaluation results

Photosensitive coloring composition initial viscosity (cp)
8
4
4
6
4
4
4
5
6
4
5
6
4
5
40 ° C / 7 days (cp)
6
4
4
6
4
4
4
6
7
4
5
7
4
5
Surface resistance (Ω/□)
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
OD (1μ/m)
1.5
1.4
1.7
1.6
1.7
1.6
1.8
1.4
1.3
1.2
1.3
1.4
1.3
1.3
Solvent resistance (maximum Abs.)
0.9
1.0
1.0
1.2
0.9
1.3
1.1
0.9
0.8
1.2
1.0
1.0
1.1
0.7
Film color hue black black black black black black black black black black black black

Table 6

Black matrix with colored resist composition example comparative example
B29
B30
B31
B32
B33
B34
B35
B36
B37
B1
B2
B3
B4
B5
Coloring Composition Example A29
Example A30
Example A31
Example A32
Example A33
Example A34
Example A35
Example A36
Example A37
Example A1
Example A2
Example A3
Example A4
Example A5
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
56.00%
Alkali soluble resin
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
8.35%
DPEHA
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
2.85%
OXE02
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
0.75%
PGMEA
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
32.0%
total
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
Pigment ratio in solid content
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.0%
35.00%
35.00%
35.0%
35.0%
Evaluation results

Photosensitive coloring composition initial viscosity (cp)
5
5
6
6
7
6
6
5
4
4
6
5
4
5
40 ° C / 7 days (cp)
5
5
7
6
8
6
6
5
4
4
8
5
4
5
Surface resistance (Ω/□)
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
1014 <
OD (1μ/m)
1.3
1.5
1.6
1.5
1.5
1.6
1.4
1.6
1.7
2.8
1.2
1.3
1.5
1.8
Solvent resistance (maximum Abs.)
0.8
1.0
1.5
1.1
1.2
1.2
2.3
1
1.5
0.2
1.2
4.0
3.5
2.5
Film color hue black black black black black black purple black black black purple brown black

<evaluation test>
With respect to the colored composition for a black matrix obtained by the above respective Examples and Comparative Examples and the colored resist composition for a black matrix, the dispersion stability, optical density, surface resistance value, solvent resistance, and coating were evaluated by the following methods. The film hue and filterability are shown in Tables 1 to 6.

(Initial viscosity, viscosity after 40 ° C / 7 days storage (dispersion stability))
The coloring composition for the black matrix of the above examples and the comparative examples and the coloring resist composition for the black matrix were separately collected in a glass bottle and stoppered, and stored at room temperature by using a B-type viscometer (manufactured by TOKIMEC Co., Ltd.). Viscosity [cp] (initial viscosity) at 25 ° C and viscosity [cp] after storage at 40 ° C for 7 days.

(surface resistance value)
Each of the black matrix coloring resist compositions in the examples and the comparative examples was applied onto a glass substrate by a spin coater at a film thickness of 1 μm, prebaked at 100 ° C for 3 minutes, and then exposed to a high pressure mercury lamp. Further, post-baking at 230 ° C for 3 hours gave a black resist pattern formed only in the solid portion. The surface resistivity of the black resist pattern of each solid portion obtained by the main body: microampere meter R8340, option: shielding box R12702A, manufactured by ADVANCE.

(OD (1 μ / m) (optical density))
The black matrix coloring resist compositions of the examples and the comparative examples were coated on a glass substrate with a film thickness of 1 μm by a spin coater, prebaked at 100 ° C for 3 minutes, exposed to a high pressure mercury lamp, and then at 230. After drying at ° C for 3 hours, a black resist pattern formed only in the solid portion was obtained. The optical density (OD value) of the obtained black resist pattern of each solid portion was measured with a Macbeth densitometer (TD-931, trade name, manufactured by Macbeth Co., Ltd.).
The OD at the eight positions was measured and corrected by the film thickness and the pigment concentration, and the average value of the OD values after the removal of the maximum and minimum values was taken as the optical density.
(The coating film is cut with a cutter to measure the film thickness at the OD value measurement point)
Corrected OD value = measured OD value × 15.0 / pigment concentration × 1.0 / measured film thickness

(solvent resistance (NMP resistance test))
Each of the black matrix coloring resist compositions of the examples and the comparative examples was applied onto a glass substrate (90 nm × 90 nm) by a spin coater at a film thickness of 1 μm, and pre-baked at 100 ° C for 3 minutes, followed by high-pressure mercury. The lamp was exposed and baked at 230 ° C for 3 hours to obtain a black resist pattern formed only in the solid portion. Next, the coated plate was placed on a plate, NMP heated to 100 ° C was added, sealed with aluminum foil, placed in an oven at 100 ° C, taken out after 10 minutes, and only the eluted solution (NMP) was recovered into the screw bottle. . After visual observation, the absorbance of the eluate (300-1000 nm, blank NMP) was measured with a spectrophotometer (UV-2500PC). The result is the recording of the maximum peak absorption. The smaller the value, the better.

(film hue)
The hue of each of the black resist patterns of the examples and the comparative examples was visually observed and the hue was evaluated.

For example, in Comparative Example A2, when only a large amount of blackening as a coloring agent is used, the coloring composition as a black matrix has a higher viscosity after being stored at 40 ° C for 7 days as compared with the initial viscosity, and the dispersion stability is deteriorated. . The viscosity in the other examples and comparative examples did not change, or was not obvious even if it was present.
According to Comparative Example B1 using only carbon black as a coloring agent, the surface resistivity and solvent resistance of the colored resist composition for a black matrix were low. According to Comparative Example B2 in which only black is used as the coloring agent, the color resist composition as a black matrix has a higher viscosity after being stored at 40 ° C for 7 days as compared with the initial viscosity, and the dispersion stability is deteriorated. The color of the film is purple instead of black. According to Comparative Example B3 using only mesoamine black as a coloring agent, as a coloring resist composition for a black matrix, solvent resistance was deteriorated, and the coating film hue was brown rather than black. According to Comparative Example B4 using indoleamine black and PB60 as a coloring agent, the solvent resistance was deteriorated as a coloring resist composition for a black matrix. According to Comparative Example B5 using carbon black, indoleamine black, PV23, and PB60 as a coloring agent, the solvent resistance was still deteriorated as a coloring resist composition for a black matrix.
On the other hand, according to Examples A1 to A37 and B1 to B37 of the examples of the present invention, dispersion stability and solvent resistance were good, surface resistance value and OD value were high, and the hue of the coating film was black. Sex film.

Claims (12)

A black coloring composition in which, as the A. coloring agent, it contains any one of the following combinations of 1 to 6: 1.a.SV49, 2.a.SV49 and b. blue and/or green pigments, 3.a.SV49, b. blue and / or green pigment, and c. purple pigment, 4.a.SV49, b. blue and / or green pigment, and e. red and / or orange pigment, 5.b1.PB60 and / or PB80, d. purple colorant, and e. red and / or orange pigment, and 6. e1. at least one selected from the group consisting of PO34, PO72, PR57:1, PR149, PR170, PR179, and PR214, b. blue and/or green pigment, and d. violet colorant. The black coloring composition as described in claim 1, wherein the A. coloring agent is as follows: b. The blue and/or green pigment is at least one selected from the group consisting of PB15:3, PB15:4, PB15:6, PB16, PB60, PB75, PB79, PB80, and PG54. Or c. purple pigment is PV23 and / or PV29, Or d. The purple colorant is at least one selected from the group consisting of PV23, PV29, and SV49. Or e. The red and/or orange pigment is selected from the group consisting of PO34, PO38, PO43, PO64, PO69, PO71, PO72, PO73, PR57:1, PR122, PR149, PR166, PR170, PR177, PR179, PR214, PR224, PR242, At least one of PR254, PR264, and PR274. The black coloring composition as described in claim 1, wherein the A. coloring agent is as follows: a. SV49 and b. blue and/or green pigment: at least one selected from the group consisting of PB15:3, PB15:4, PB15:6, PB16, PB60, PB80 and PG54, Or a.SV49, b. blue and/or green pigment: at least one selected from the group consisting of PB15:3, PB15:4, PB15:6, PB16, PB60, PB80 and PG54, and c. Purple pigment: PV23 and / Or PV29, Or a.SV49, b. blue and/or green pigment: at least one selected from the group consisting of PB15:3, PB15:4, PB15:6, PB16, PB60, PB80 and PG54, and e. red and/or orange pigment : at least one selected from the group consisting of PO34, PO38, PO43, PO64, PO69, PO71, PO72, PO73, PR57:1, PR122, PR149, PR166, PR170, PR177, PR179, PR214, PR224, PR242, PR254, PR264, and PR274 , Or e1.PO34, PO72, b. Blue and/or green pigment: at least one selected from the group consisting of PG15, PG16, PB60, PB80 and PG54, and d. Purple colorant: PV23, PV29 and/or SV49. The black colored composition according to any one of claims 1 to 3, wherein the A. coloring agent contains carbon black and/or indoleamine black. The black coloring composition according to any one of claims 1 to 4, which contains: B. a dispersing aid having a sulfonic acid group, C. dispersant, D. Adhesive resin, and E. Organic solvent. The black coloring composition according to any one of the items 1 to 5, which contains the F. polyfunctional epoxy compound. The black coloring composition according to claim 5, wherein the dispersing aid having a sulfonic acid group is a compound represented by the following formula (1) and/or (2) and/or a pigment yellow 138. Sulfonide, Wherein X and Y are the same or different and represent a phenyl group which may be substituted by F, C1, Br, NO ₂ , CH ₃ or OCH ₃ , and M represents H, Na, K, NH ₄ or NR1R2R3R4, wherein R1, R2 R3 and R4 are the same or different and each represents a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by another substituent or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted by another substituent, m Indicates an integer of 1 or more. The black colored composition according to claim 6, wherein X of the compound represented by the formula (1) and/or (2) is 2,5-dichlorophenyl group, and Y is a phenyl group. The black coloring composition according to claim 5, wherein the C. dispersing agent is a basic group-containing acrylic resin-based dispersing agent. The black coloring composition according to claim 6, wherein the F. polyfunctional epoxy compound has a skeleton selected from the group consisting of a diphenylmethane skeleton, a dinaphthylene skeleton, a triazine skeleton, a novolac skeleton, and a tetraphenylethane skeleton. A polyfunctional epoxy compound having at least one skeleton of a bisphenol skeleton and a biphenyl skeleton. The black colored composition according to claim 5, wherein the D. binder resin contains an alkali-soluble resin. A black coloring resist composition containing the black coloring composition, the alkali-soluble resin, the photopolymerizable compound, and the photopolymerization initiator according to any one of the items 1 to 11.