JP2021173972A - Black matrix pigment dispersion composition, black matrix resist composition, and black matrix - Google Patents

Abstract

To provide a black matrix pigment dispersion composition which offers superior developability of a back matrix resist composition and allows for producing a black matrix having a superior surface resistance even after going through prolonged high-temperature post-baking.SOLUTION: A black matrix pigment dispersion composition is provided, containing a black colorant, a pigment dispersant, an oxazine compound, and an organic solvent, where the pigment dispersant is an acrylic block copolymer containing nitrogen atoms.SELECTED DRAWING: None

Description

The present invention relates to a pigment dispersion composition for a black matrix, a resist composition for a black matrix, and a black matrix.

In an image display device using a liquid crystal or plasma, a light-shielding film (a light-shielding film on the outside light side of the TFT, etc. Black matrix) is provided.
Then, in the liquid crystal display device, the leakage light mainly from the backlight is prevented from being reflected on the screen, and in the plasma display device, the bleeding mainly due to the turbidity of each color light is prevented from being reflected on the screen, and the display characteristics (contrast and color purity) are improved. Helping to improve.

For example, in a color filter used to convert white light of a backlight of a liquid crystal display device into colored light, red, green, and blue are usually formed on the surface of a transparent substrate such as glass or plastic sheet on which a black matrix is formed. It is manufactured by a method of sequentially forming pixels having different hues in a pattern such as a stripe shape or a mosaic shape.

In addition, a color filter having a black matrix formed as a light-shielding film is also used in a touch panel that combines an image display device and a position input device. It was generally done to form on the side. However, as the demand for weight reduction of the touch panel increases, the development of a technology for simultaneously forming a light-shielding film and a touch sensor on the same side of the cover glass is progressing so that the weight can be further reduced.

For example, Patent Document 1 states that a black colorant, an alkali-soluble resin having a carboxyl group, a photopolymerization initiator, an organic solvent, and a polyvalent oxazine compound having a plurality of oxazine rings in the molecule are contained. A characteristic black matrix resist composition is disclosed.

In Patent Document 1, a carbodiimide-based pigment dispersant is used as the pigment dispersant.
When the above-mentioned carbodiimide-based pigment dispersant is used in a resist composition for a black matrix containing a polyvalent oxazine compound, the obtained black matrix has an excellent surface resistance value, but the developability of the resist composition for a black matrix is lowered. There was a challenge.

On the other hand, in a resist composition for a black matrix containing a polyvalent oxazine compound, when a pigment dispersant (for example, a urethane-based pigment dispersant) generally used conventionally is used, the resist composition for a black matrix is used. Although there is no problem with the developability of the product, there is a problem that the surface resistance value of the obtained black matrix is lowered.

Further, in recent years, image display devices have come to be used in various situations such as mobile applications.
With the expansion of applications of such image display devices, a more robust black matrix is required.

As a method of making the black matrix more robust, a method of performing post-baking at a high temperature for a long time may be used.
However, the conventional pigment dispersion for black matrix has a problem that the surface resistance value decreases when post-baking is performed at a high temperature for a long time, and there is room for improvement.

Japanese Unexamined Patent Publication No. 2003-344996

Therefore, the present invention is a pigment dispersion composition for a black matrix, which is excellent in developability of a resist composition for a black matrix and can form a black matrix having an excellent surface resistance value even after post-baking at a high temperature for a long time. The purpose is to provide.

The present inventors contain a black colorant, a pigment dispersant, an oxazine compound, and an organic solvent, and the pigment dispersant is a black block copolymer containing a nitrogen atom. We have found that a pigment dispersion composition for a black matrix can be obtained, which has excellent developability of a resist composition for a matrix and can form a black matrix having an excellent surface resistance value even after post-baking at a high temperature for a long time. , The present invention has been completed.

That is, the present invention is characterized in that it contains a black colorant, a pigment dispersant, an oxazine compound, and an organic solvent, and the pigment dispersant is an acrylic block copolymer containing a nitrogen atom. It is a pigment dispersion composition for a black matrix.

〔一般式（１）中、Ｒ^１及びＲ^２は、不飽和結合を有してもよいアルキル基又はアリール基を表し、相互に同一であっても異なってもよい。Ｘ^１は２価の連結基である。
一般式（２）中、Ｒ^３及びＲ^４は、不飽和結合を有してもよいアルキル基又はアリール基を表し、相互に同一であっても異なってもよい。Ｘ^２は２価の連結基である。〕
また、上記黒色着色剤は、カーボンブラックを含むことが好ましい。
また、上記カーボンブラックは、酸性カーボンブラックであることが好ましい。
本発明は、本発明のブラックマトリックス用顔料分散組成物から得られるブラックマトリックス用レジスト組成物でもある。
本発明は、本発明のブラックマトリックス用レジスト組成物から形成されるブラックマトリックスでもある。
以下、本発明のブラックマトリックス用顔料分散組成物、ブラックマトリックス用レジスト組成物、及び、それにより形成されるブラックマトリックスについて詳細に説明する。 It is preferable that the pigment dispersion composition for black matrix of the present invention further contains a pigment dispersion aid.
Further, the pigment dispersion aid is preferably a sulfonated phthalocyanine compound.
Further, the oxazine compound is preferably a compound represented by the following general formulas (1) and / or (2).

[In the general formula (1), R ¹ and R ² represent an alkyl group or an aryl group which may have an unsaturated bond, and may be the same as or different from each other. X ¹ is a divalent linking group.
In the general formula (2), R ³ and R ⁴ represent an alkyl group or an aryl group which may have an unsaturated bond, and may be the same as or different from each other. X ² is a divalent linking group. ]
Further, the black colorant preferably contains carbon black.
Further, the carbon black is preferably acidic carbon black.
The present invention is also a black matrix resist composition obtained from the black matrix pigment dispersion composition of the present invention.
The present invention is also a black matrix formed from the resist composition for a black matrix of the present invention.
Hereinafter, the pigment dispersion composition for black matrix of the present invention, the resist composition for black matrix, and the black matrix formed thereby will be described in detail.

<Pigment dispersion composition for black matrix>
The pigment dispersion composition for a black matrix of the present invention contains a black colorant, an epoxy resin, an oxazine compound, and an organic solvent, and the epoxy resin has an aromatic ring.

(Black colorant)
The pigment dispersion composition for a black matrix of the present invention contains a black colorant.
The black colorant preferably contains carbon black, and more preferably the carbon black is acidic carbon black.
The carbon black preferably has an average primary particle diameter of 20 to 60 nm, and more preferably a neutral carbon black having an average primary particle diameter of 20 to 60 nm and / or an acidic carbon black having an average primary particle diameter of 20 to 60 nm.
If the primary particle size of the black colorant is smaller than 20 nm or larger than 60 nm, it may not have sufficient light-shielding properties or may be inferior in storage stability.
The average primary particle diameter is the value of the arithmetic mean diameter observed by electron microscopy.

When the above neutral carbon black and acidic carbon black are used in combination, the mixing ratio (mass ratio) of the neutral carbon black and the acidic carbon black is preferably 85/15 to 15/85, and 75/25 to 40/85. 60 is more preferable.
If the ratio of neutral carbon black of the above carbon black is more than 85/15, the seal strength may decrease, and if the ratio of acidic carbon black is more than 15/85, the development margin and fine line adhesion decrease. I have something to do.

The above-mentioned acidic carbon black and neutral carbon black will be described.
Carbon black can be roughly divided into acidic carbon and neutral carbon according to the surface structure. Acidic carbon is a carbonaceous substance that has been originally or artificially oxidized, and exhibits acidity when mixed with distilled water and boiled. On the other hand, neutral carbon is known to exhibit a neutral or higher pH when mixed and boiled with distilled water.

The neutral carbon black preferably has a pH in the range of 8.0 to 10.0, and specifically, Printex 25 manufactured by Orion Engineered Carbons Co., Ltd. (average primary particle size 56 nm, pH 9.5). , Printex 35 (average primary particle size 31 nm, pH 9.5), Printex 65 (average primary particle size 21 nm, pH 9.5), MA # 20 manufactured by Mitsubishi Chemical Co., Ltd. (average primary particle size 40 nm, pH 8.0). , MA # 40 (average primary particle size 40 nm, pH 8.0), MA # 30 (average primary particle size 30 nm, pH 8.0) and the like.

The acidic carbon black preferably has a pH in the range of 2.0 to 4.0. Specifically, Raven 1080 (average primary particle size 28 nm, pH 2.4) and Raven 1100 (average primary particle size) manufactured by Columbia Chemicals Co., Ltd. 32 nm, pH 2.9), MA-8 (average primary particle size 24 nm, pH 3.0) manufactured by Mitsubishi Chemical Co., Ltd., MA-100 (average primary particle size 22 nm, pH 3.5), manufactured by Orion Engineered Carbons Co., Ltd. Special Black 250 (average primary particle size 56 nm, pH 3.0), Special Black 350 (average primary particle size 31 nm, pH 3.0), Special Black 550 (average primary particle size 25 nm, pH 4.0) and the like can be mentioned.

The black colorant is preferably Special Black 250 from the viewpoint of preferably imparting pigment dispersibility and surface resistance value.

The pH is 25 ° C. using a glass electrode after adding 1 g of carbon black to 20 ml of distilled water (pH 7.0) from which carbon dioxide has been removed and mixing with a magnetic stirrer to prepare an aqueous suspension. It can be measured with (German industrial product standard DIN ISO 787/9).

The content of the black colorant is preferably 3 to 70% by mass, more preferably 10 to 50% by mass, as a mass fraction of the pigment dispersion composition for black matrix of the present invention with respect to the total solid content.
If the content of the black colorant is less than 3% by mass, the light-shielding property when the black matrix is formed may be low, and if it exceeds 70% by mass, it may be difficult to disperse the pigment.

(Pigment dispersant)
The pigment dispersion composition for black matrix of the present invention contains a pigment dispersant. The pigment dispersant is an acrylic block copolymer containing a nitrogen atom.
By containing the pigment dispersant and the oxazine compound described later, the oxazine compound is polymerized by the high temperature at the time of post-baking to become a high molecular weight compound, so that the black color is colored in the coating film softened by the high temperature. Even if the agent moves, the polymer of the oxazine compound acts as a spacer so that the black colorants do not come into contact with each other.
Further, since the pigment dispersant is strongly adsorbed on the black colorant, it acts as a spacer like the polymer of the oxazine compound, so that the black colorants do not come into contact with each other.
Therefore, it is presumed that the resist composition for black matrix of the present invention could secure a high surface resistance value by not forming a conductive structure structure.
However, the present invention does not have to be construed as being limited to this mechanism of action.

As the acrylic block copolymer containing a nitrogen atom, those disclosed in JP-A-2019-35970 and the production method can be appropriately selected and used.
Specifically, the acrylic block copolymer containing a nitrogen atom has an A block having at least one of a quaternary ammonium base and an amino group in the side chain, and a quaternary ammonium base and an amino group. It is preferably composed of no B blocks, and more preferably at least one of an AB block copolymer and a BAB block copolymer.

The amine value of the acrylic block copolymer containing a nitrogen atom is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g.
The amine value is a value expressed by the number of mg of KOH corresponding to the molar equivalent of the acid required to neutralize the amino group in 1 g of the acrylic block copolymer.

Regarding the molecular weight of the acrylic block copolymer containing a nitrogen atom, the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably 1000 to 40,000, more preferably 2000 to 20000.

Examples of commercially available products of the acrylic block copolymer containing a nitrogen atom include BYK-LPN21116, BYK-2000, BYK-LPN6919, BYK-LPN21324, and BYK-LPN22012 (all manufactured by Big Chemie).

The content of the pigment dispersant is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the black colorant.

〔一般式（１）中、Ｒ^１及びＲ^２は、不飽和結合を有してもよいアルキル基又はアリール基を表し、相互に同一であっても異なってもよい。Ｘ^１は２価の連結基である。
一般式（２）中、Ｒ^３及びＲ^４は、不飽和結合を有してもよいアルキル基又はアリール基を表し、相互に同一であっても異なってもよい。Ｘ^２は２価の連結基である。〕 (Oxazine compound)
The pigment dispersion composition for black matrix of the present invention contains an oxazine compound.
The oxazine compound is preferably a compound represented by the following general formulas (1) and / or (2).

[In the general formula (1), R ¹ and R ² represent an alkyl group or an aryl group which may have an unsaturated bond, and may be the same as or different from each other. X ¹ is a divalent linking group.
In the general formula (2), R ³ and R ⁴ represent an alkyl group or an aryl group which may have an unsaturated bond, and may be the same as or different from each other. X ² is a divalent linking group. ]

R ¹ and R ² , and R ³ and R ⁴ are alkyl or aryl groups that may have unsaturated bonds.
The alkyl group may be, for example, linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, and an n-butyl group. It has an isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, etc., and an unsaturated bond derived from cashew nut shell liquid (CNSL). A good alkyl group and the like can be mentioned.

Examples of the aryl group include a tolyl group, a xsilyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group and the like.

X ¹ and X ² are divalent linking groups.
The divalent linking group includes a linear or branched alkylene group having 1 to 12 carbon atoms and -CH constituting the alkylene group, in addition to the linking groups represented by the following formulas (3) to (5). _{One or more of 2} − is substituted with −O−, −S−, −NH−, a urethane group, a urea group, an amide group, a siloxane bond which may have a substituent, or −CO−. Examples include valuation linking groups.

^{As the oxazine compound represented by the general formula (1), R 1} and R ² are phenyl groups and X ¹ is the above formulas (3) to (5) from the viewpoint of forming a black matrix having a high surface resistance value. ) Is preferably one of the linking groups.
Further, as the oxazine compound represented by the above general formula (2), R ³ and R ⁴ are H and X ² is a methylenedioxy group or a methylenedioxy group from the viewpoint of forming a black matrix having a high surface resistance value. It is preferable that R ³ and R ⁴ are an alkyl group that may have an unsaturated bond derived from cashew nut shell liquid (CNSL), and X ² is an ethylene group.

As a method for obtaining the oxazine compound, a known method can be used, and for example, the methods described in JP-A-2000-178332, JP-A-2003-344996 and the like can be used.

The content of the oxazine compound is the total solid content of the pigment dispersion composition for black matrix of the present invention from the viewpoint of preferably forming a black matrix in which the surface resistance value does not decrease even after post-baking at a high temperature for a long time. The lower limit is preferably 0.1% by mass, the lower limit is more preferably 0.5% by mass, the lower limit is further preferably 1% by mass, and the lower limit is 3% by mass. Is particularly preferable, and the lower limit is most preferably 5% by mass.
The upper limit of the content of the oxazine compound is 30 as the mass fraction of the pigment dispersion composition for black matrix of the present invention with respect to the total solid content from the viewpoint of ensuring the optical concentration derived from the pigment concentration in the black matrix. It is preferably mass%, the upper limit is more preferably 25% by mass, the upper limit is even more preferably 20% by mass, and the upper limit is particularly preferably 15% by mass.

(Organic solvent)
The pigment dispersion composition for black matrix of the present invention contains an organic solvent.
As the organic solvent, an organic solvent conventionally used in the field of liquid crystal black matrix resist can be preferably used.

Specifically, the organic solvent includes an ester-based organic solvent, an ether-based organic solvent, an ether ester-based organic solvent, and a ketone-based organic solvent having a boiling point of 100 to 250 ° C. at ^{normal pressure (1.013 × 10 2 kPa).} , Aromatic hydrocarbon-based organic solvent, nitrogen-containing organic solvent, etc.
When a large amount of an organic solvent having a boiling point of more than 250 ° C. is contained, a coating film formed by applying the black matrix resist composition obtained from the black matrix pigment dispersion composition of the present invention is prebaked. In addition, the organic solvent may not evaporate sufficiently and remains in the dry coating film, which may reduce the heat resistance of the dry coating film.
Further, if a large amount of the organic solvent having a boiling point of less than 100 ° C. is contained, it becomes difficult to apply the coating film evenly and uniformly, and a coating film having excellent surface smoothness may not be obtained.

Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol mono. Ether-based organic solvents such as ethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate. , Ethylene ester-based organic solvents such as propylene glycol monoethyl ether acetate; ketone-based organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, δ-butyrolactone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2, -Ethyl hydroxy-2-methylpropionate, 3-methyl-3-methoxybutyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Ester-based organic solvents such as ethyl ethoxyacetate, ethyl hydroxyacetate, n-amyl formate; alcohol-based solvents such as methanol, ethanol, isopropyl alcohol and butanol; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethyl Examples thereof include nitrogen-containing organic solvents such as acetoamide. These can be used alone or in admixture of two or more.

Among the above organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate are used in terms of solubility, dispersibility, coatability, etc. , Cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate and the like are preferable, and propylene glycol is preferable. More preferably, it is monomethyl ether or propylene glycol monomethyl ether acetate.

(Pigment dispersion aid)
The pigment dispersion composition for black matrix of the present invention preferably contains a pigment dispersion aid.
In the above-mentioned pigment dispersion aid, in the process of making the black colorant into fine particles and dispersing the black colorant, the basic skeleton portion is adsorbed on the pigment surface and the acid group enhances the affinity with the organic solvent and the pigment dispersant, thereby increasing the above-mentioned black color. It has the effect of improving the fineness of the colorant during dispersion and the stability of dispersion over time after dispersion. Further, it is more preferable that the black colorant dispersion aid itself is dissolved in an organic solvent or dispersed in fine particles because it can be adsorbed over a wider range on the surface of the black colorant.

Examples of the pigment dispersion aid include phthalocyanine compounds having an acid group, anthraquinone compounds having an acid group, and naphthalene compounds having an acid group.
Among them, a phthalocyanine compound having an acid group is preferable from the viewpoint of dispersibility of the black colorant.

Examples of the acid group include a sulfonic acid group, a carboxyl group, a phosphoric acid group and the like.
Among them, a sulfonic acid group is preferable from the viewpoint of imparting a surface resistance value to the black matrix from the viewpoint of dispersing the black colorant.

Examples of commercially available phthalocyanine compounds having an acid group include BYK-2100 (manufactured by Big Chemie) and Solsparse 5000 (manufactured by Lubrizol).

The content of the pigment derivative is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the black colorant.

(Pigment dispersion composition for black matrix)
The pigment dispersion composition for black matrix of the present invention preferably has a viscosity of 10 mPa · s or less, more preferably 8 mPa · s or less, and further preferably 6 mPa · s or less.
The viscosity means the viscosity measured at 25 ° C. using an E-type viscometer (R100 type viscometer model RE100L manufactured by Toki Sangyo Co., Ltd.).

The pigment dispersion composition for black matrix of the present invention has a viscosity change rate [(viscosity after storage-viscosity before storage) / (viscosity before storage)] of 10% or less before and after storage at 40 ° C. for 1 month. It is preferably 8% or less, more preferably 6% or less.

(Method for Producing Pigment Dispersion Composition for Black Matrix)
The method for producing a pigment dispersion composition for black matrix of the present invention can be obtained by adding the above-mentioned various components, mixing and kneading.
The method for kneading the meat is not particularly limited, and for example, a bead mill, a ready mill, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, a nanomizer, etc. It may be used and kneaded by a known method.

<Resist composition for black matrix>
The present invention is also a black matrix resist composition obtained from the black matrix pigment dispersion composition of the present invention.

(Pigment dispersion composition for black matrix)
The resist composition for black matrix of the present invention contains the pigment dispersion composition for black matrix of the present invention described above.
The content of the pigment dispersion composition for black matrix is preferably 30 to 80% by mass, preferably 40 to 75% by mass, based on the total mass of the resist composition for black matrix of the present invention. More preferred.

(Photopolymerization initiator)
The resist composition for black matrix of the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can generate radicals and cations by being irradiated with active energy rays such as ultraviolet rays and electron beams, and is, for example, 1- [9-ethyl. -6- (2-Methylbenzoyl) -9H-Carbazole-3-yl] -1- (O-Acetyloxym) Etanone, benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy- 4'-Dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexylphenylketone, t -Butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzophenoneone, 1,4-dimethylanthraquinone, Examples include benzophenone-based agents such as 2-phenylanthraquinone and 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, and photopolymerization initiators such as thioxanthone-based, anthraquinone-based, and triazine-based. Be done.
The photopolymerization initiator may be used alone or in combination of two or more.

The content of the photopolymerization initiator is preferably 1 to 20% by mass as a mass fraction with respect to the total solid content of the resist composition for black matrix of the present invention.

(Photopolymerizable compound)
The resist composition for black matrix of the present invention preferably contains a photopolymerizable compound.
Examples of the photopolymerizable compound include a monomer having one or more photopolymerizable unsaturated bonds in the molecule, an oligomer having a photopolymerizable unsaturated bond, and the like.

Examples of the monomer having one photopolymerizable unsaturated bond in the molecule include alkyl methacrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, or acrylates and benzyl methacrylates. Aralkyl methacrylate or acrylate such as benzyl acrylate, alkoxyalkyl methacrylate or acrylate such as butoxyethyl methacrylate and butoxyethyl acrylate, aminoalkyl methacrylate or acrylate such as N, N-dimethylaminoethyl methacrylate and N, N-dimethylaminoethyl acrylate, diethylene glycol Methacrylate or acrylic acid ester of polyalkylene glycol monoalkyl ether such as monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, methacrylic acid ester of polyalkylene glycol monoaryl ether such as hexaethylene glycol monophenyl ether Alternatively, acrylic acid ester, isobonyl methacrylate or acrylate, glycerol methacrylate or acrylate, 2-hydroxyethyl methacrylate or acrylate and the like can be used.

Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, and glycerol dimethacrylate. , Neopentyl glycol dimethacrylate, Polyethylene glycol dimethacrylate, Polypropylene glycol dimethacrylate, Tetraethylene glycol dimethacrylate, Trimethylol propantrimethacrylate, Pentaarislitol trimethacrylate, Pentaerythritol tetramethacrylate, Dipentaerythritol tetramethacrylate, Dipentaerythritol Hexamethacrylate, dipentaerythritol pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate , Polypropylene glycol diacrylate, Tetraethylene glycol diacrylate, Trimethylol propantriacrylate, Pentaarislitol triacrylate, Pentaerythritol tetraacrylate, Dipentaerythritol tetraacrylate, Dipentaerythritol hexaacrylate, Dipentaerythritol pentaacrylate, etc. be able to.

As the oligomer having a photopolymerizable unsaturated bond, one obtained by appropriately polymerizing the above-mentioned monomer can be used.
The above photopolymerizable compound can be used alone or in combination of two or more.

The content of the photopolymerizable compound is preferably 3 to 50% by mass as a mass fraction with respect to the total solid content of the resist composition for black matrix of the present invention.

(Alkali-soluble resin)
The resist composition for black matrix of the present invention preferably contains an alkali-soluble resin.
The alkali-soluble resin acts as a binder for the black colorant and is soluble in a developing solution, particularly an alkali developing solution, which is used in the developing process when producing a black matrix. Is preferable.

The alkali-soluble resin may be a block copolymer. By adopting a block copolymer, the pigment dispersibility is improved as compared with other copolymers, and solubility in PGMEA or an alkaline developer can be imparted.
Among the block copolymers, the block copolymer having a block composed of an ethylenically unsaturated monomer having one or more carboxyl groups and a block composed of another copolymerizable ethylenically unsaturated monomer is co-weighted. Coalescence is preferred.

The block copolymer is not particularly limited, and conventionally used block copolymers can be used. Among them, specifically, styrene and 2-hydroxyethyl which can be copolymerized with an ethylenically unsaturated monomer having a carboxyl group such as acrylic acid and methacrylic acid and an ethylenically unsaturated monomer having a carboxyl group. Acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide, polystyrene macromonomer, polymethylmethacrylate macromonomer, carboepoxy Examples thereof include a copolymer with at least one ethylenically unsaturated monomer selected from the group of monomers such as diacrylate and oligomers.
However, it is desirable not to use N-vinylpyrrolidone or a sulfur element-containing monomer.
As the block copolymer, a block resin synthesized by living radical polymerization or anionic polymerization can be adopted.
A part of the block portion of the block copolymer may be composed of a random copolymer.

As the alkali-soluble resin, an alkali-soluble cardo resin can also be adopted.
Examples of the alkali-soluble cardo resin include an epoxy (meth) acrylate acid adduct having a fluorene skeleton, which is an addition product of a fluorene epoxy (meth) acrylic acid derivative and a dicarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. Can be mentioned.
Further, the present alkali-soluble resin may have a photopolymerizable functional group.

The acid value of the alkali-soluble resin is preferably 5 to 300 mgKOH / g, more preferably 5 to 250 mgKOH / g, further preferably 10 to 200 mgKOH / g, and particularly preferably 60 to 150 mgKOH / g from the viewpoint of development characteristics.
In the present specification, the acid value is a theoretical acid value, which is a value calculated mathematically based on the ethylenically unsaturated monomer having a carboxyl group and its content.

The weight average molecular weight of the alkali-soluble resin is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and 5,000 to 30,000 from the viewpoint of development characteristics and solubility in an organic solvent. Is even more preferable.
In the present invention, the weight average molecular weight is a polystyrene-equivalent weight average molecular weight obtained based on GPC.
In the present specification, Water2690 (manufactured by Waters) is used as the device for measuring the weight average molecular weight, and PLgel 5 μm MIXED-D (manufactured by Agilent Technologies) is used as the column.

The content of the alkali-soluble resin is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the black colorant.
In this case, if the content of the alkali-soluble resin is less than 1 part by mass, the development characteristics may deteriorate, and if the content of the alkali-soluble resin exceeds 200 parts by mass, the concentration of the black colorant is relative. Therefore, it may be difficult to achieve the desired color density as a thin film.

The alkali-soluble resin preferably does not contain any of the primary, secondary, and tertiary amino groups, and further does not contain a quaternary ammonium group. Furthermore, it is more preferable that it does not have a basic group.
An alkali-soluble resin having a structure other than the block copolymer may be blended as long as the effect of the present invention is not impaired.

(Organic solvent)
As the organic solvent, the organic solvent described in the above-mentioned pigment dispersion composition for black matrix of the present invention can be appropriately selected and used.

The content of the organic solvent is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, based on the total mass of the resist composition for black matrix of the present invention.

(Other additives)
In the resist composition for black matrix of the present invention, various additives such as a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant can be appropriately used, if necessary.

(Resist composition for black matrix)
The resist composition for black matrix of the present invention has excellent solubility in a developing solution.
The resist composition for black matrix of the present invention is applied onto a glass substrate (Corning 1737) with a spin coater so as to have a thickness of 1 μm, prebaked at 100 ° C. for 3 minutes, and then developed at 23 ° C. (potassium hydroxide). It is preferable that it is easily dissolved when immersed in (0.05 mass% aqueous solution).

The resist composition for black matrix of the present invention is excellent in developability.
The developability can be tested by the following method.
The pigment-dispersed resist composition for black matrix is applied onto a glass substrate (Corning 1737) with a spin coater so as to have a film thickness of 1 μm, and prebaked at 100 ° C. for 3 minutes.
Then, using a photomask having a line pattern of 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, and 30 μm, exposure is performed with ^{a high-pressure mercury lamp at a UV integrated light intensity of 400 mJ / cm 2.}
Then, it is immersed in a developing solution (0.05 mass% aqueous solution of potassium hydroxide) at 23 ° C., and the time (break point) at which the developing pattern begins to appear is measured at a shower developing pressure of ^{0.5 kgf / cm 2.}
At this time, the resist composition for black matrix in the portion of the photomask is preferably completely removed within 60 seconds, more preferably completely within 45 seconds, and completely within 30 seconds. It is more preferable that it is removed.

(Manufacturing method of resist composition for black matrix)
As a method for producing a resist composition for black matrix of the present invention, for example, the pigment dispersion composition for black matrix of the present invention is prepared, and then the remaining materials are added and stirred and mixed using a stirrer or the like. Can be made.
The method of stirring and mixing is not particularly limited, and known methods such as an ultrasonic disperser, a high-pressure emulsifier, a bead mill, three rolls, a sand mill, and a kneader can be used.
When preparing the resist composition for black matrix of the present invention, the black colorant, the pigment dispersant, the oxazine compound, and the above described in the pigment dispersion composition for black matrix of the present invention are required. A pigment dispersion aid or the like may be added.

<Black Matrix>
The black matrix of the present invention is formed from the resist composition for black matrix of the present invention.

The method for forming the black matrix of the present invention is not particularly limited. For example, the resist composition for black matrix of the present invention is applied onto a transparent substrate and dried to form a coating film, and then a photomask is formed on the coating film. A mask is placed, and a black matrix can be formed through the photomask by a method such as image exposure, development, and if necessary, photocuring.

As a method for applying, drying, exposing and developing the resist composition for black matrix of the present invention, a known method can be appropriately selected.
Further, as the transparent substrate, a known transparent substrate such as a glass substrate or a plastic substrate can be appropriately selected and used.

The thickness of the coating film after drying is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, and even more preferably 1 to 4 μm.
By setting the thickness within the range, a predetermined pattern can be suitably developed, and a predetermined optical density can be preferably imparted.

The black matrix of the present invention is applied onto a glass substrate (Corning 1737), prebaked at 100 ° C. for 3 minutes, exposed with a high-pressure mercury lamp (UV integrated light amount 400 mJ / cm ² ), and post-baked at 230 ° C. for 3 hours. The surface resistance value when a resist pattern having a thickness of 1 μm is formed ^{is preferably 5.0 × 10 9} Ω / □ or more, more preferably 1.0 × 10 ¹⁰ Ω / □ or more, and 1.0 × 10 ¹¹ Ω / □ or more is more preferable, 5.0 × 10 ¹¹ Ω / □ or more is particularly preferable, and 1.0 × 10 ¹² Ω / □ or more is most preferable.
The surface resistance value can be measured with a main body: micro ammeter R8340 and an option: shield box R12702A (both manufactured by Advance Co., Ltd.).

Since the pigment dispersion composition for black matrix, the resist composition for black matrix, and the black matrix of the present invention have the above-mentioned characteristics, they can be suitably used as a black matrix for an image display device, a touch panel, or the like.

According to the present invention, a black matrix resist composition has excellent developability, and a black matrix pigment dispersion composition capable of forming a black matrix having an excellent surface resistance value even after post-baking at a high temperature for a long time. Can provide things.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto as long as it does not deviate from the gist and scope of application. Unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass", respectively, in this embodiment.

The various materials used in the following examples and comparative examples are as follows.
<Black colorant>
(Carbon black 1)
Acidic carbon black, product name "SPECIAL BLACK 250", average primary particle size 56 nm, pH 3.0, manufactured by Orion Engineered Carbons (Carbon Black 2)
Neutral carbon black, product name "Printex35", average primary particle size 31 nm, pH 9.5, manufactured by Orion Engineered Carbons <Pigment Dispersant>
(Pigment Dispersant 1)
Product name "BYK-LPN21116", an acrylic AB block copolymer consisting of an A block having a quaternary ammonium base and an amino group in the side chain and a B block having no quaternary ammonium base and an amino group. Solid content 40%, manufactured by Big Chemie (pigment dispersant 2)
Product name "BYK-2000", acrylic AB block copolymer consisting of A block having a quaternary ammonium base in the side chain and B block having no quaternary ammonium base, solid content 40%, big chemie Manufactured by the company (pigment dispersant 3)
In a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring rod, and a thermometer, 50.0 parts of a carbodiimide equivalent 316 polycarbodiimide compound having an isocyanate group and a molecular weight of 1000 poly (3-methylpentyl adipate) 115.7 parts of diol is charged and held at about 100 ° C. for 5 hours to react an isocyanate group with a hydroxyl group, and then 84.6 parts of a ring-opened polymer of a polycaprolactone having a molecular weight of 2000 and having a carboxyl group at the terminal is charged. After reacting the carbodiimide group and the carboxyl group at about 100 ° C. for 2 hours, 375.5 parts of propylene glycol monomethyl ether acetate was added to the solution of the pigment dispersant 3 having an average molecular weight of about 4200 and a carbodiimide equivalent of 1583. (Solid content 40%) was obtained.
(Pigment Dispersant 4)
Product name "DISPERBYK-167", urethane pigment dispersant, solid content 52%, manufactured by Big Chemie <Pigment dispersion aid>
(Pigment Dispersion Aid 1)
Product name "BYK-2100", sulfonated phthalocyanine compound, manufactured by Big Chemie (pigment dispersion aid 2)
Product name "Solsperse 5000", sulfonated phthalocyanine compound, manufactured by Lubrizol (pigment dispersion aid 3)
30 ml of concentrated sulfuric acid was placed in a 100 ml Erlenmeyer flask, and C.I. I. 10 g of Pigment Red 2 was added, and the mixture was stirred at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was placed in a 1 L beaker, the above reaction was poured into the ice water, and the mixture was stirred with a magnetic stirrer for 30 minutes. This was filtered and washed with water under reduced pressure, and the obtained solid was dried to obtain C.I. I. 12 g of a sulfonate of Pigment Red 2 (pigment dispersion aid 3) was obtained.
<Oxazine compound>
(Oxazine compound 1)
In the above general formula (2), ^{an oxazine compound in which R 3} and R ⁴ are H and X ² is represented by a methylenedioxy group (trade name "JBZ-OP100N", manufactured by JFE Chemical Co., Ltd.).
(Oxazine compound 2)
In the above general formula (1) ^{, an oxazine compound in which R 1} and R ² are phenyl groups and X ¹ is a linking group represented by the above formula (3) is described in a known method (Japanese Patent Laid-Open No. 2000-178332). Method).
(Oxazine compound 3)
In the above general formula (2), R ³ and R ⁴ are alkyl groups that may have an unsaturated bond derived from cashew nut shell liquid (CNSL), and X ² is an oxazine compound represented by an ethylene group (trade name). "CR-276", manufactured by Tohoku Kako Co., Ltd.)
<Organic solvent>
PM (Propylene Glycol Monomethyl Ether)
PGMEA (Propylene Glycol Monomethyl Ether Acetate)
<Photopolymerizable compound>
DPHA (dipentaerythritol hexaacrylate)
<Photopolymerization initiator>
OXE02 (Product name "Irgacure OXE02", 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) etanone, manufactured by BASF)
<Alkali-soluble resin>
WR-301 (Product name "WR-301", cardo resin, acid value 100 mgKOH / g, solid content 45%, manufactured by ADEKA Corporation)

<Preparation of pigment dispersion composition for black matrix>
The above-mentioned black colorants, pigment dispersants 1 to 4, pigment dispersion aids 1 to 3, oxazine compounds 1 to 3 and an organic solvent are mixed so as to have the composition shown in Table 1, and kneaded with a bead mill for a whole day and night for black matrix. A pigment dispersion composition was prepared.

<Evaluation test>
(viscosity)
The viscosity of the black matrix pigment dispersion composition prepared in Examples and Comparative Examples was measured at 25 ° C. using an E-type viscometer (R100 type viscometer model RE100L manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 1.

(Viscosity change rate)
The black matrix pigment dispersion compositions prepared in Examples and Comparative Examples were stored at 40 ° C. for 1 month.
Before and after the above storage, the viscosity at 25 ° C. was measured using an E-type viscometer (R100 type viscometer model RE100L manufactured by Toki Sangyo Co., Ltd.), and the viscosity change rate [(viscosity after storage-viscosity before storage). ) / (Viscosity before storage)] was determined and evaluated according to the following criteria. The results are shown in Table 1.
◯: The viscosity change rate before and after storage was 10% or less.
X: The rate of change in viscosity before and after storage exceeded 10%.

Using a high-speed stirrer, the pigment dispersion composition for black matrix and other materials (photopolymerizable compound, alkali-soluble resin, photopolymerization initiator and organic solvent) were uniformly mixed so as to have the composition shown in Table 2. Then, it was filtered through a filter having a pore size of 3 μm to obtain a black matrix resist composition of Examples and Comparative Examples.

<Evaluation test>
(Surface resistance value)
The pigment-dispersed resist composition for each black matrix of Examples and Comparative Examples was applied on a glass substrate (Corning 1737) with a spin coater so as to have a film thickness of 1 μm, prebaked at 100 ° C. for 3 minutes, and then with a high-pressure mercury lamp. The mixture was exposed and post-baked at 230 ° C. for 3 hours to prepare a black resist pattern formed only of the solid portion.
The surface resistance value of each of the produced black resist patterns was measured with a main body: micro ammeter R8340 and an option: shield box R12702A (both manufactured by Advance). The results are shown in Table 2.

(Developer solubility)
The pigment-dispersed resist composition for each black matrix of Examples and Comparative Examples was applied onto a glass substrate (Corning 1737) with a spin coater so as to have a film thickness of 1 μm, prebaked at 100 ° C. for 3 minutes, and then 23 ° C. Was immersed in the developing solution (0.05 mass% aqueous solution of potassium hydroxide), and the dissolved state was visually evaluated. The results are shown in Table 2.

(Developability)
The pigment-dispersed resist compositions for Black Matrix of Examples and Comparative Examples were applied onto a glass substrate (Corning 1737) with a spin coater so as to have a film thickness of 1 μm, and prebaked at 100 ° C. for 3 minutes.
Then, using a photomask having a line pattern of 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, and 30 μm, exposure was performed with a ^{UV integrated light intensity of 400 mJ / cm 2 using a high-pressure mercury lamp.}
Then, it was immersed in a developing solution (0.05 mass% aqueous solution of potassium hydroxide) at 23 ° C., and the time (breakpoint) at which the developing pattern began to appear was measured at a shower developing pressure of ^{0.5 kgf / cm 2.} It was evaluated according to the following criteria. The results are shown in Table 2.
◯: The black matrix resist composition in the photomask portion could be completely removed within 30 seconds.
Δ: The black matrix resist composition in the photomask portion could be completely removed within 60 seconds over 30 seconds.
X: The black matrix resist composition in the photomask portion cannot be completely removed even after 60 seconds.

From the examples, a black colorant, a pigment dispersant, an oxazine compound, and an organic solvent are contained.
By using a pigment dispersion composition for black matrix, which is an acrylic block copolymer containing a nitrogen atom, the pigment dispersant has excellent developability of the resist composition for black matrix, and has a high temperature and a long time. It was confirmed that a black matrix having an excellent surface resistance value can be formed even after post-baking.
On the other hand, in Comparative Example 1 using the carbodiimide-based pigment dispersant, the developer was inferior in solubility (peeled without being dissolved) and was also inferior in developability. Further, in Comparative Example 2 in which the urethane pigment dispersant was used and Comparative Example 3 in which the oxazine compound was not used, it was confirmed that the surface resistance value at high temperature and for a long time was not sufficient.

According to the present invention, a black matrix resist composition has excellent developability, and a black matrix pigment dispersion composition capable of forming a black matrix having an excellent surface resistance value even after post-baking at a high temperature for a long time. Can provide things.

Claims (8)

Contains a black colorant, a pigment dispersant, an oxazine compound, and an organic solvent.
A pigment dispersion composition for a black matrix, wherein the pigment dispersant is an acrylic block copolymer containing a nitrogen atom. The pigment dispersion composition for a black matrix according to claim 1, further comprising a pigment dispersion aid. The pigment dispersion composition for a black matrix according to claim 2, wherein the pigment dispersion aid is a sulfonated phthalocyanine compound. The pigment dispersion composition for a black matrix according to any one of claims 1 to 3, wherein the oxazine compound is a compound represented by the following general formulas (1) and / or (2).

[In the general formula (1), R ¹ and R ² represent an alkyl group or an aryl group which may have an unsaturated bond, and may be the same as or different from each other. X ¹ is a divalent linking group.
In the general formula (2), R ³ and R ⁴ represent an alkyl group or an aryl group which may have an unsaturated bond, and may be the same as or different from each other. X ² is a divalent linking group. ] The pigment dispersion composition for a black matrix according to any one of claims 1 to 4, wherein the black colorant contains carbon black. The pigment dispersion composition for a black matrix according to claim 5, wherein the carbon black is an acidic carbon black. A black matrix resist composition obtained from the black matrix pigment dispersion composition according to any one of claims 1 to 6. A black matrix formed from the resist composition for black matrix according to claim 7.