JP7564294B2 - Colored composition and colored resist composition - Google Patents

Description

The present invention relates to a colored composition and a colored resist composition containing the same.

In recent years, coloring compositions for black matrices have been used in a wide variety of applications. For example, in flat panel displays such as liquid crystal and plasma displays, they are used to provide a light-shielding film (black matrix) in the gaps between colored patterns in the display area of the screen and around the edges of the display area, and in liquid crystal displays using TFTs, they are used on the external light side of the TFT. In liquid crystal displays, they mainly prevent light leakage from the backlight from being reflected on the screen, and in plasma displays, they mainly prevent bleeding caused by the turbidity of each color of light from being reflected on the screen, thereby improving display characteristics (contrast and color purity).

For example, color filters used to convert the white light of a liquid crystal display backlight into colored light are usually manufactured by forming pixels of different hues, red, green, and blue, in sequence in a striped or mosaic pattern on the surface of a transparent substrate, such as glass or a plastic sheet, on which a black matrix has been formed.

Furthermore, in touch panels that combine an image display device and a position input device, color filters with black matrices formed thereon are also used as light-shielding films, and up until now, this has typically been formed on the side opposite the sensor substrate, sandwiching a cover glass between them. However, as the demand for lighter touch panels increases, progress is being made in the development of technology to simultaneously form the light-shielding film and touch sensor on the same side of the cover glass, which will enable even lighter panels.

For example, Patent Document 1 discloses a technology for imparting shielding properties, etc., to a photosensitive coloring composition for forming color spacers by using a combination of a specific pigment and carbon black as colorants and setting the carbon black content within a specific range.

For example, Patent Document 2 discloses a technology that maintains light blocking properties and the voltage holding rate of liquid crystal by appropriately combining pigment types with different light absorption characteristics to ensure a balance between light absorption in the ultraviolet and visible regions.

However, when the solvent resistance of a coloring composition such as a black matrix constituting a liquid crystal layer of an image display device is low, problems occur such as cracks or chips in the pixel pattern and elution of the coloring component from the pixel pattern.
In the above-mentioned techniques, no consideration has been given to solvent resistance, and there has been a demand for the development of a black matrix colored composition that can provide a black resist pattern having excellent solvent resistance.

JP 2016-177190 A International Publication No. 2013/115268

The present invention aims to provide a colored composition capable of obtaining a black resist pattern having excellent light-shielding properties and solvent resistance, and a colored resist composition containing the same.

The inventors discovered that by using a combination of specific pigments in a coloring composition containing a pigment and a binder resin, a coloring composition can be obtained that can produce a black resist pattern that has excellent shielding properties and excellent solvent resistance, and thus completed the present invention.

That is, the present invention relates to a coloring composition for black matrices, which comprises a pigment and a binder resin, and the pigment comprises at least one selected from the group consisting of C.I. Pigment Orange 16 and C.I. Pigment Yellow 139, and C.I. Pigment Blue 60.

In addition, it is preferable that the pigment further contains one or more pigments selected from the group consisting of C. I. Pigment Violet 23 and C. I. Pigment Violet 29.
The present invention also relates to a colored resist composition produced by using the colored composition of the present invention.
The colored composition of the present invention or the colored resist composition of the present invention is also used as a black matrix, a black column spacer, or a black partition wall material.
The colored composition of the present invention and the colored resist composition containing the same will be described in detail below.

(Pigment)
The coloring composition of the present invention contains a pigment selected from the group consisting of C.I. Pigment Orange 16 and C.I. Pigment Yellow 139, and C.I. Pigment Blue 60.
By using the above pigment, a coloring composition for black matrix can be obtained that can obtain a black resist pattern that is excellent in light shielding and solvent resistance. From the viewpoint of imparting solvent resistance, it is preferable that the above pigment contains C.I. Pigment Yellow 139 and C.I. Pigment Blue 60.

The content of one or more pigments selected from the group consisting of C.I. Pigment Orange 16 and C.I. Pigment Yellow 139 is preferably 5 to 60% by mass, more preferably 8 to 50% by mass, even more preferably 10 to 45% by mass, and particularly preferably 10 to 40% by mass, based on the total amount of pigments, from the viewpoint of light-shielding properties.
From the viewpoint of light-shielding properties, the content of C.I. Pigment Blue 60 is preferably 5 to 70 mass%, more preferably 10 to 60 mass%, further preferably 15 to 55 mass%, and particularly preferably 20 to 50 mass%, based on the total mass of the pigment.

It is preferable that the pigment further contains one or more pigments selected from the group consisting of C. I. Pigment Violet 23 and C. I. Pigment Violet 29.
By further containing one or more pigments selected from the group consisting of C.I. Pigment Violet 23 and C.I. Pigment Violet 29, it is possible to impart excellent shielding properties to the black resist pattern obtained by the colored composition.
From the viewpoint of imparting solvent resistance, it is more preferable that the pigment contains C.I. Pigment Violet 29.

The content of one or more pigments selected from the group consisting of C.I. Pigment Violet 23 and C.I. Pigment Violet 29 is preferably 1 to 70% by mass, and more preferably 10 to 60% by mass, based on the total amount of pigments, from the viewpoint of light-shielding properties.

In the coloring composition of the present invention, the pigment is preferably present in an amount of 20 to 90% by mass, and more preferably 30 to 80% by mass, based on the total solid content.

In the coloring composition of the present invention, the above pigment may contain other pigments such as carbon black, red pigments, orange pigments, blue pigments, and green pigments, as long as the effects of the present invention are not impaired.

(Binder resin)
The coloring composition of the present invention contains a binder resin.
The binder resin can be used without any particular limitation as long as it is a resin that can be used as a component of a color filter, and examples of the binder resin include an alkali-soluble resin, a thermosetting resin, a thermoplastic resin, a photopolymerizable compound (a photopolymerizable resin, a monomer or oligomer having one or more photopolymerizable unsaturated bonds in the molecule, etc.), etc. These can be used alone or in combination of two or more kinds.
In the colored composition of the present invention, the binder resin is preferably contained in an amount of 1 to 40% by mass, and more preferably 3 to 25% by mass, based on the total solid content.

Examples of the alkali-soluble resin include an alkali-soluble copolymer and an alkali-soluble cardo resin.
Examples of the alkali-soluble copolymer include copolymers obtained by reacting a carboxyl group-containing unsaturated monomer such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, citraconic acid, citraconic anhydride, or citraconic acid monoalkyl ester with at least one selected from the group consisting of styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol methacrylate, mono(meth)acrylate having a dicyclopentadiene skeleton, N-phenylmaleimide, polystyrene macromonomer, and polymethyl methacrylate macromonomer, and epoxy acrylate resins.

Examples of the alkali-soluble cardo resin include epoxy (meth)acrylate acid adducts having a fluorene skeleton, which are addition products of fluorene epoxy (meth)acrylic acid derivatives and dicarboxylic acid anhydrides and/or tetracarboxylic acid dianhydrides.
The above alkali-soluble resins can be used alone or in combination of two or more kinds. From the viewpoint of film-forming property and alkaline developability, the alkali-soluble resin preferably has an acid value of 40 to 200 mgKOH/g and a weight average molecular weight of 1,000 to 50,000.
The above alkali-soluble resins can be used alone or in combination of two or more kinds depending on the required performance.

Examples of the above-mentioned thermosetting resins and thermoplastic resins include butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, phenolic resins, polyester resins, acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclized rubbers, epoxy resins, celluloses, polybutadiene, polyimide resins, polyamideimide resins, benzoguanamine resins, melamine resins, urea resins, etc.

The photopolymerizable resin may be a resin in which a photocrosslinkable group such as a (meth)acrylic compound or cinnamic acid is introduced via an isocyanate group, aldehyde group, epoxy group, or the like to a linear polymer having reactive substituents such as hydroxyl groups, carboxyl groups, or amino groups. Polymers in which a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth)acrylic compound having a hydroxyl group such as a hydroxyalkyl (meth)acrylate may also be used.

In the photopolymerizable compound, examples of monomers having one photopolymerizable unsaturated bond in the molecule include alkyl methacrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; aralkyl methacrylates or acrylates such as benzyl methacrylate and benzyl acrylate; alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate; N,N-dimethylaminoethyl methacrylate and N,N-dimethylaminoethyl methacrylate. Examples of the methacrylic acid esters include aminoalkyl methacrylates or acrylates such as noethyl acrylate; methacrylic acid esters or acrylic acid esters of polyalkylene glycol alkyl ethers such as diethylene glycol ethyl ether, triethylene glycol butyl ether, and dipropylene glycol methyl ether; methacrylic acid esters or acrylic acid esters of polyalkylene glycol aryl ethers such as hexaethylene glycol phenyl ether; isobornyl methacrylate or acrylate; glycerol methacrylate or acrylate; and 2-hydroxyethyl methacrylate or acrylate.

In the photopolymerizable compound, examples of monomers 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, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethate, and bisphenol A dimethacrylate. Examples of such acrylates include 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, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate.

(Carbon Black)
The colored composition of the present invention may contain carbon black from the viewpoint of adjusting the color tone.
Examples of the carbon black include acetylene black, channel black, furnace black, and ketjen black.
Specific examples of the carbon black include MA7, MA8, MA11, MA14, #1000, #2350, etc., manufactured by Mitsubishi Chemical Corporation; SpecialBlack 350, SpecialBlack 250, SpecialBlack 550, NEROX 2500, NEROX 3500, NEROX 305, etc., manufactured by Orion Engineered Carbons; MOGUL, manufactured by Cabot Corporation; L, REGAL400R, TPK1101R, TPK1104R, TPK1227R, etc., and RAVEN1200, RAVEN1250, RAVEN1255, RAVEN1190U, RAVEN1170, RAVEN1035, RAVEN1080U, RAVEN1060U, RAVEN1100U, etc. manufactured by Columbian Carbon Co., Ltd.
Among these, acidic carbon black having a pH of 5 or less and an acidic group such as a carboxyl group is preferred, and the particle size is preferably 20 to 60 nm.
Examples of acidic carbon black that satisfies the above conditions include NEROX 2500, NEROX 3500, TPK1101R, TPK1104R, and TPK1227R.
The particle size refers to an average primary particle size measured or calculated by observation with a microscope.

The content of the acidic carbon black is not particularly limited, but is preferably 70% by mass or less based on the mass of the total pigment of the coloring composition of the present invention. If the content of the acidic carbon black exceeds 70% by mass, the voltage holding ratio and the exposure sensitivity may decrease.
A more preferable upper limit of the content of the acidic carbon black is 50% by mass based on the mass of all pigments in the coloring composition of the present invention.
The colored composition of the present invention may not contain the acidic carbon black.

The coloring composition of the present invention preferably further contains a pigment dispersant, a pigment dispersant represented by the general formula (1) and/or (2) described later, and/or a pigment dispersant which is a sulfonated copper phthalocyanine (which may be neutralized), and/or a pigment dispersant which is a sulfonated C.I. Pigment Yellow 138 (which may be neutralized), a binder resin, and an organic solvent.

(Pigment Dispersant)
The coloring composition of the present invention preferably contains a pigment dispersant.
The pigment dispersant is a basic group-containing pigment dispersant, and examples of the pigment dispersant that can be used include anionic surfactants, basic group-containing polyester-based pigment dispersants, basic group-containing acrylic-based pigment dispersants, basic group-containing urethane-based pigment dispersants, basic group-containing carbodiimide-based pigment dispersants, and acidic group-containing polymeric pigment dispersants.
These basic group-containing pigment dispersants may be used alone or in combination of two or more kinds. Among them, basic group-containing polymeric pigment dispersants are preferred because they provide good pigment dispersibility.

Specific examples of the basic group-containing polymeric pigment dispersant include:
(1) A reaction product of an amino group and/or an imino group of a polyamine compound (e.g., a poly(lower alkylene amine) such as polyallylamine, polyvinylamine, or polyethylene polyimine) with at least one member selected from the group consisting of polyesters, polyamides, and polyesteramides having a free carboxyl group (JP 2001-59906 A),
(2) Reaction products of low molecular weight amino compounds such as poly(lower) alkyleneimines and methyliminobispropylamine with polyesters having free carboxyl groups (JP-A-54-37082, JP-A-01-311177),
(3) A reaction product obtained by sequentially reacting an isocyanate group of a polyisocyanate compound with an alcohol such as methoxypolyethylene glycol, a polyester having one hydroxyl group such as caprolactone polyester, a compound having two to three isocyanate group-reactive functional groups, and an aliphatic or heterocyclic hydrocarbon compound having an isocyanate group-reactive functional group and a tertiary amino group (JP Patent Publication No. 02-612);
(4) A compound obtained by reacting a polymer of an acrylate having an alcoholic hydroxyl group with a polyisocyanate compound and a hydrocarbon compound having an amino group.
(5) A reaction product obtained by adding a polyether chain to a low molecular weight amino compound.
(6) A reaction product obtained by reacting a compound having an isocyanate group with a compound having an amino group (JP-A-04-210220);
(7) 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 (JP-A-09-87537).
(8) A reaction product of a polycarbonate compound having a functional group capable of reacting with an amino group at one end with a polyamine compound (JP-A-09-194585),
(9) Copolymers of at least one selected from methacrylic acid esters or acrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, stearyl acrylate, and benzyl acrylate, at least one basic group-containing polymerizable monomer such as acrylamide, methacrylamide, N-methylolamide, vinylimidazole, vinylpyridine, and a monomer having an amino group and a polycaprolactone skeleton, and at least one styrene, styrene derivative, and other polymerizable monomer (JP Patent Publication (Kokai) No. 01-164429),
(10) Basic group-containing carbodiimide pigment dispersants (International Publication WO04/000950),
(11) Block copolymers consisting of a block having a basic group such as a tertiary amino group or a quaternary ammonium salt group and a block having no functional group (see the description in JP-A-2005-55814)
(12) A pigment dispersant obtained by subjecting a polyallylamine to a Michael addition reaction with a polycarbonate compound (JP-A-09-194585);
(13) Carbodiimide-based compound having at least one polybutadiene chain and at least one basic nitrogen-containing group (JP 2006-257243 A),
(14) Carbodiimide compounds having at least one amide group-containing side chain and at least one basic nitrogen-containing group in the molecule (JP-A-2006-176657).
(15) A polyurethane-based compound having a structural unit having an ethylene oxide chain and a propylene oxide chain, and having an amino group quaternized with a quaternizing agent (JP 2009-175613 A),
(16) A compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule with an active hydrogen group of a compound having an active hydrogen group in the molecule and having a carbazole ring and/or an azobenzene skeleton, wherein the number of carbazole rings and azobenzene skeletons in the molecule of the compound is 15 to 85% of the total number of isocyanate groups derived from the isocyanate compound having an isocyanurate ring and urethane bonds and urea bonds generated by the reaction of the isocyanate groups with the active hydrogen groups (Japanese Patent Application No. 2009-220836).
(17) Graft copolymers in which polyether or polyester side chains are introduced into acrylate polymers having amino groups.

Among the above basic group-containing polymeric pigment dispersants, basic group-containing urethane-based polymeric pigment dispersants, basic group-containing polyester-based polymeric pigment dispersants, and basic group-containing acrylic-based polymeric pigment dispersants are more preferred, and amino group-containing urethane-based polymeric pigment dispersants, amino group-containing polyester-based polymeric pigment dispersants, and amino group-containing acrylic-based polymeric pigment dispersants are even more preferred. Among the above basic group-containing polymeric pigment dispersants, basic group (amino group)-containing polymeric pigment dispersants having at least one chain selected from the group consisting of polyester chains, polyether chains, and polycarbonate chains are particularly preferred.

In the coloring composition of the present invention, the pigment dispersant is preferably present in an amount of 1 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the pigment.

〔式中、Ｘ及びＹは、同一若しくは異なって、Ｆ、Ｃｌ、Ｂｒ、ＮＯ_２、ＣＨ_３又はＯＣＨ_３で置換されていてもよいフェニル基を表す。Ｍは、Ｈ、Ｎａ、Ｋ、ＮＨ_４又はＮＲ^１Ｒ^２Ｒ^３Ｒ^４（Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、同一若しくは異なって、他の置換基で置換されていてもよい炭素数１～１０の飽和若しくは不飽和の脂肪族炭化水素基、又は、他の置換基で置換されていてもよい炭素数６～１０の芳香族炭化水素基を表す。）を表す。ｍは、１以上の整数を表す。〕 (Pigment Dispersion Aid)
The coloring composition of the present invention preferably contains a pigment dispersing aid represented by the following general formula (1) and/or (2), and/or a pigment dispersing aid which is a sulfonated product of copper phthalocyanine (which may be neutralized), and/or a pigment dispersing aid which is a sulfonated product of C.I. Pigment Yellow 138 (which may be neutralized).

[In the formula, X and Y are the same or different and represent a phenyl group which may be substituted with F, Cl, Br, NO ₂ , CH ₃ or OCH _3. M represents H, Na, K, NH ₄ or NR ¹ R ² R ³ R ⁴ (R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with other substituents, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with other substituents). m represents an integer of 1 or more.]

The pigment dispersing aid is used to disperse the pigment.
When dispersing the pigment, the pigment dispersion assistant and the pigment dispersant are used in combination, thereby making it possible to obtain excellent fluidity and stability over time. In addition, when the colored composition is used as a colored resist composition, it becomes possible to obtain a high optical density.

In the above general formulas (1) and (2), Y and Z are the same or different and represent a phenyl group which may be substituted with F, Cl, Br, _NO2 , _CH3 or _OCH3 . M represents H, ^{Na , K} , _NH4 or ^NR1R2R3R4 .
With respect to "NR ¹ R ² R ³ R ⁴ " (M) in the above general formulas (1) and (2), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with other substituents, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with other substituents. Here, examples of the saturated or unsaturated aliphatic hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl and decyl groups; alkenyl groups such as vinyl, allyl and 1-butenyl groups; and alkynyl groups such as ethynyl and propynyl groups. Examples of the aromatic hydrocarbon group include phenyl and naphthyl groups. Examples of the other substituents include a hydroxyl group, a halogen atom, a carboxyl group, an amino group, and a lower alkyl group (having 1 to 5 carbon atoms).
Incidentally, one of R ¹ , R ² , R ³ and R ⁴ may be substituted with another substituent, or two or more of them may be substituted with other substituents.
Furthermore, "m" in the above general formulas (1) and (2) is an integer of 1 or more.

In the above compound (pigment dispersing aid), the compound represented by the above general formula (1) is an enol tautomer, and the compound represented by the above general formula (2) is a keto tautomer, and both compounds are included in the above pigment dispersing aid. In other words, the above pigment dispersing aid includes both the case of a compound represented by the above general formula (1) or (2), and the case of a compound consisting of both the above general formulas (1) and (2).

Such pigment dispersion aids are novel compounds and can be produced, for example, by dissolving monoazo compounds of the following formulas (3) to (30) in concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or a mixture thereof, heating to room temperature or 80 to 90°C, and then diluting with a large amount of water to obtain a suspension, filtering, washing with water, and drying and pulverizing the obtained filter cake; no commercially available products exist.

Among these pigment dispersion aids, a compound represented by the following general formula (31) (a compound obtained by the above-mentioned manufacturing method using the monoazo compound of the above-mentioned formula (3): enol type) and/or a compound represented by the following general formula (32) (a compound obtained by the above-mentioned manufacturing method using the monoazo compound of the above-mentioned formula (4): keto type) in which Y in the above-mentioned general formula (1) and/or (2) is a 2,5-dichlorophenyl group and Z is a phenyl group is preferred, as they have good fluidity and stability over time and can provide a colored resist composition with a higher level of optical density.

In the colored composition of the present invention, the amount of the pigment dispersion aid is preferably 30 parts by mass or less, and more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the pigment.
Even if the amount of the pigment dispersion aid exceeds 30 parts by mass relative to 100 parts by mass of the pigment, the pigment dispersion effect may not be improved.

(Organic Solvent)
The coloring composition of the present invention preferably contains an organic solvent.
As the organic solvent, preferred are ester- ^based organic solvents, ether-based organic solvents, ether ester-based organic solvents, ketone-based organic solvents, aromatic hydrocarbon-based organic solvents, nitrogen-containing organic solvents, and the like, each of which has a boiling point of 70 to 300° C. at normal pressure (1.013×10 2 kPa).

Specific examples of such solvents include ether-based organic solvents such as 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, propylene glycol monoethyl 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, and propylene glycol monoethyl ether acetate. Examples of suitable organic solvents include ether ester organic solvents such as pyrene glycol monoethyl ether acetate, ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone, ester organic solvents such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetic acid ester, and n-amyl formate, and nitrogen-containing organic solvents such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These organic solvents can be used alone or in combination of two or more.

Among these organic solvents, in terms of boiling point, solubility, dispersibility, coatability, etc., diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, etc. are preferred, with propylene glycol monomethyl ether acetate being more preferred.

(Other additives)
Depending on the method for producing the colored composition of the present invention, various additives such as a photopolymerization initiator, a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant can be appropriately used.
The photopolymerization initiator is not particularly limited, but examples thereof include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzil dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, triazine-based photopolymerization initiators, oxime ester-based photopolymerization initiators, etc. These photopolymerization initiators can be used alone or in combination of two or more.
In the colored composition of the present invention, the content of the photopolymerization initiator is preferably 0.1 to 10% by mass, and more preferably 0.5 to 4% by mass, based on the total solid content.

<Method of producing colored composition>
An example of a method for producing a colored composition using the above materials will be described below.
For each of the pigments of the above colors, a binder resin, carbon black, a pigment dispersant, a pigment dispersing aid, an organic solvent and other additives are added as necessary and mixed to obtain a mixture.
The resulting mixture is kneaded and dispersed using various dispersing machines such as a roll mill, kneader, high-speed stirrer, bead mill, ball mill, sand mill, ultrasonic dispersing machine, and high-pressure dispersing machine to obtain a pigment dispersion composition of each color.
Next, the pigment dispersion compositions of each color obtained are blended in a predetermined combination so as to produce a pseudo-black color, and a binder resin, an organic solvent, and other additives are added as necessary, and the mixture is uniformly mixed using a stirring device such as a high-speed stirrer, and then filtered through a filter to obtain the colored composition of the present invention. In the above-mentioned production method, the binder resin can be added when preparing the pigment dispersion composition. Alternatively, the binder resin can be added after preparing the pigment dispersion composition, when preparing the colored composition.

(Covariance)
A mixture is obtained by mixing the pigments so as to give a pseudo-black color, a pigment dispersant, a pigment dispersion aid, an organic solvent, and optionally a binder resin, and optionally other additives. The mixture is kneaded and dispersed using various dispersing machines such as a roll mill, a kneader, a high-speed stirring machine, a bead mill, a ball mill, a sand mill, an ultrasonic dispersing machine, and a high-pressure dispersing machine, to obtain a pigment dispersion composition.
Next, a binder resin, an organic solvent, and other additives are added to the obtained pigment dispersion composition as necessary, and the mixture is uniformly mixed using a stirring device such as a high-speed stirrer, and then filtered through a filter to obtain the colored composition of the present invention. In the above-mentioned production method, the binder resin can be added when the pigment dispersion composition is produced.
Alternatively, after preparing the pigment dispersion composition, the pigment may be added when preparing the colored composition.

The colored composition of the present invention preferably has a viscosity measured at 25° C. of 2.0 to 20.0 mPa·s.
If the viscosity is less than 2.0 mPa·s or exceeds 20.0 mPa·s, the coatability may be adversely affected.
The above viscosity is measured by sealing the colored composition of the present invention in a glass bottle or the like and storing it for one day, using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).

The colored composition of the present invention preferably has a temporal stability of 0.8 to 1.1.
If the temporal stability is less than 0.8 or exceeds 1.1, the coating property and developability may be adversely affected.
The above-mentioned stability over time was measured by measuring the viscosity at 25° C. after the colored composition of the present invention was sealed in a glass bottle or the like and stored at room temperature (25° C.) for one day, and the viscosity at 25° C. after the colored composition of the present invention was sealed in a glass bottle or the like and stored at 40° C. for seven days, using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), and was calculated as (viscosity after storage at 40° C. for 7 days)/(viscosity after storage at room temperature for 1 day).

Next, an example in which the colored composition of the present invention is used as a colored resist composition will be described.
The colored resist composition of the present invention includes the colored composition of the present invention.
The colored resist composition of the present invention is preferably one that is composed of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and an organic solvent in addition to the colored composition of the present invention, and is obtained by appropriately adding various additives such as a polymerization inhibitor as necessary.

<Constituent Materials of Colored Resist Composition>
(Coloring composition)
The colored resist composition of the present invention is produced using the colored composition of the present invention.
The content of the colored composition of the present invention is, in mass fraction, preferably from 20 to 90 mass %, and more preferably from 30 to 80 mass %, relative to the total solid content of the colored resist composition of the present invention.

(Pigment Dispersant)
As the pigment dispersant, those described above in relation to the colored composition of the present invention can be suitably used.
In the colored resist composition of the present invention, the content of the pigment dispersant is preferably from 0.1 to 50 parts by mass, and more preferably from 1 to 20 parts by mass, relative to 100 parts by mass of the total pigments used.

(Binder resin)
As the binder resin, those described in the colored composition of the present invention can be suitably used.
In the colored resist composition of the present invention, the content of the binder resin is preferably from 3 to 50 mass % based on the solid content of the colored resist composition of the present invention.

(Photopolymerization initiator)
The photopolymerization initiator is not particularly limited, but examples thereof include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzil dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, triazine-based photopolymerization initiators, and oxime ester-based photopolymerization initiators. These photopolymerization initiators can be used alone or in combination of two or more.
In the colored composition of the present invention, the content of the photopolymerization initiator is preferably 0.1 to 10% by mass, and more preferably 0.5 to 6% by mass, based on the total solid content.

(Photopolymerizable monomer)
As the photopolymerizable monomer, an ethylenically unsaturated compound or the like is used. The ethylenically unsaturated compound used here is preferably a compound having two or more ethylenically unsaturated bonds in the molecule in terms of polymerizability, crosslinkability, etc. These photopolymerizable monomers can be used alone or in combination of two or more kinds.

(Organic Solvent)
As the organic solvent, those described in relation to the colored composition of the present invention can be suitably used.
In the colored resist composition of the present invention, the content of the organic solvent is preferably from 5 to 90 mass % relative to the total amount of the colored resist composition of the present invention, from the viewpoints of the solubility of each material, pigment dispersibility, coatability, etc.

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

<Method of producing the colored resist composition of the present invention>
The method for producing the colored resist composition of the present invention is one example of a preferred embodiment of the present invention, and the present invention is not limited thereto.
For example, a method can be used in which a binder resin, a photopolymerizable compound, a photopolymerization initiator, an organic solvent, and other additives are added to the colored composition of the present invention, and the mixture is stirred and mixed using a stirring device or the like.

The colored resist composition of the present invention preferably has a viscosity measured at 25° C. of 1.0 to 30.0 mPa·s.
If the viscosity is less than 1.0 mPa·s or exceeds 30.0 mPa·s, the coatability may be adversely affected.
The above viscosity is measured by sealing the colored resist composition of the present invention in a glass bottle or the like and storing it for one day, and then measuring the viscosity using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).

The colored resist composition of the present invention preferably has a temporal stability of 0.8 to 1.2.
If the stability over time is less than 0.8 or more than 1.2, it may have a detrimental effect on coatability and developability. The stability over time is measured by measuring the viscosity at 25°C after the colored resist composition of the present invention is sealed in a light-shielding glass bottle or the like and stored at a low temperature (5°C) for 1 day, and the viscosity at 25°C after the colored composition of the present invention is sealed in a light-shielding glass bottle or the like and stored at a low temperature (5°C) for 7 days using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), and is calculated as (viscosity after storage at 5°C for 7 days)/(viscosity after storage at 5°C for 1 day).

The colored resist composition of the present invention preferably has an optical density (OD value) of 1.00 or more, and more preferably 1.20 or more, when a resist pattern with a thickness of 1 μm is formed.
If the optical density (OD value) is 1.25 or more, it can be said that the shielding property is sufficient.
The optical density (OD value) mentioned above is a value measured by forming a 1 μm resist pattern using the colored resist composition of the present invention and using a Macbeth densitometer (TD-931, product name, manufactured by Macbeth Corporation).

[0046] The colored resist composition of the present invention, when a cured coating film having a thickness of 2 µm is formed, preferably has a solvent resistance of 0.6 or less, more preferably 0.5 or less, even more preferably 0.4 or less, particularly preferably 0.3 or less, and most preferably 0.2 or less.
The solvent resistance was measured by immersing a 2 μm-thick cured coating film in N-methylpyrrolidone heated to 100° C. and incubating the film for 10 minutes in an oven at 100° C. After that, the absorbance of the N-methylpyrrolidone was measured with a spectrophotometer (UV-2500PC), and the maximum peak absorbance was taken as the solvent resistance value.

The colored composition and colored resist composition of the present invention have the above-mentioned properties, and therefore can be suitably used as a black matrix, black column spacer, or black partition wall material for image display devices, touch panels, and the like.

The present invention provides a colored composition that has excellent light-shielding properties and solvent resistance, and a colored resist composition that contains the same.

The present invention will be specifically described below using examples, but the present invention is not limited to these as long as it does not deviate from the spirit and scope of application. In the examples, unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

The materials of the coloring compositions used in the following Examples and Comparative Examples are as follows.
<Pigments>
P.V. 23 (C.I. Pigment Violet 23)
P.V. 29 (C.I. Pigment Violet 29)
P.V. 32 (C.I. Pigment Violet 32)
P.Y. 139 (C.I. Pigment Yellow 139)
P.Y. 185 (C.I. Pigment Yellow 185)
P.O. 16 (C.I. Pigment Orange 16)
P.O. 64 (C.I. Pigment Orange 64)
P.R. 254 (C.I. Pigment Red 254)
P.B.60 (C.I. Pigment Blue 60)
P.B. 15:6 (C.I. Pigment Blue 15:6)
<Carbon black>
TPK1104R (manufactured by Cabot, oil absorption: 38ml/100g, pH: 2.7)
<Binder resin>
BzMA/MAA (alkali-soluble resin, benzyl methacrylate/methacrylic acid copolymer, theoretical acid value: 120 mg KOH/g, mass average molecular weight: 10,000)
<Pigment dispersant>
BYK-LPN-22102 (BYK-Chemie, an acrylic block copolymer consisting of a segment having a pigment affinity group and a segment having a binder compatibility group)
<Pigment Dispersion Aid>
A 100 ml Erlenmeyer flask was charged with 30 ml of concentrated sulfuric acid, and 10 g of Pigment Red 2 (a 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 mixture of 50 g of water and 50 g of ice was placed in a 1 L beaker, and the above reaction product was poured into the ice water and 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 12 g of Pigment Dispersing Aid 1 (a compound represented by the above general formula (31) and/or (32): M=H).
<Organic Solvent>
PGMEA (Propylene glycol monomethyl ether acetate)

The materials of the colored resist compositions used in the following Examples and Comparative Examples are as follows.
<Binder resin>
SPC-3500 (alkali-soluble resin, containing carbon-carbon unsaturated bonds, theoretical acid value: 60 mg KOH/g, mass average molecular weight: 11,000)
<Photopolymerization initiator>
A 1:1 mixture of Irgacure 907 (manufactured by BASF, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one) and Irgacure OXE02 (manufactured by BASF, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)) <photopolymerizable monomer>
DPEHA (photopolymerizable compound, dipentaerythritol hexaacrylate)
<Organic Solvent>
PGMEA (Propylene glycol monomethyl ether acetate)

<Preparation of Colored Compositions of Examples 1 to 10 and Comparative Examples 1 to 3>
Various materials were mixed to obtain the composition shown in Table 1 (the amount of each material in Table 1 is expressed as mass %) and milled overnight in a bead mill to prepare colored compositions of Examples 1 to 10 and Comparative Examples 1 to 3.

<Preparation of Colored Resist Compositions of Examples 11 to 20 and Comparative Examples 4 to 6>
Using a high-speed stirrer, each of the colored compositions of Examples 1 to 10 and Comparative Examples 1 to 3 was uniformly mixed with other materials to give the composition shown in Table 2 (the amount of each material used in Table 2 is mass %), and then filtered through a filter having a pore size of 3 μm to obtain colored resist compositions of Examples 11 to 20 and Comparative Examples 4 to 6.

(Evaluation test)
The colored compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 3, and the colored resist compositions obtained in Examples 11 to 20 and Comparative Examples 4 to 6 were evaluated for fluidity and stability over time by the following method, and the results are shown in Tables 1 and 2.
Furthermore, the colored resist compositions obtained in Examples 11 to 20 and Comparative Examples 4 to 6 were coated to form resist patterns, and the optical density and solvent resistance thereof were evaluated. The results are shown in Table 2.

<Liquidity>
The colored compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were each placed in a glass bottle, sealed, and stored at room temperature (25°C) for one day. Then, the viscosity [mPa s] at 25°C was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) to evaluate the fluidity.
The colored resist compositions obtained in Examples 11 to 20 and Comparative Examples 4 to 6 were each placed in a light-shielding glass bottle, sealed, and stored at low temperature (5°C) for one day, and then the viscosity [mPa s] at 25°C was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) to evaluate the fluidity.

<Stability over time>
The colored compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were each placed in a glass bottle, and the colored compositions of the present invention were sealed in a glass bottle or the like, and the viscosity at 25° C. after storing at room temperature (25° C.) for one day, and the viscosity at 25° C. after storing the colored compositions of the present invention in a sealed glass bottle or the like at 40° C. for seven days were measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), and the viscosity was calculated as (viscosity after storage at 40° C. for 7 days)/(viscosity after storage at room temperature for one day).
In addition, for the colored resist compositions obtained in Examples 11 to 20 and Comparative Examples 4 to 6, the viscosities at 25°C after storing in a light-shielding glass bottle or the like at a low temperature (5°C) for one day, and the viscosities at 25°C after storing in a light-shielding glass bottle or the like at a low temperature (5°C) for seven days were measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), and the viscosity was calculated as (viscosity after storing at 5°C for 7 days)/(viscosity after storing at 5°C for one day).

<Optical Density (OD value)>
The colored resist compositions of Examples 11 to 20 and Comparative Examples 4 to 6 were applied to a glass substrate using a spin coater to a film thickness of 1 μm, prebaked at 100° C. for 3 minutes, exposed to a high pressure mercury lamp, and further postbaked at 230° C. for 30 minutes to obtain black resist patterns formed only in solid areas. The optical density (OD value) of each of the obtained black resist patterns in the solid areas was measured using a Macbeth densitometer (TD-931, product name, manufactured by Macbeth Co., Ltd.).

<Solvent resistance>
Each of the colored resist compositions of Examples 11 to 20 and Comparative Examples 4 to 6 was applied onto a glass substrate by a spin coater to a film thickness of 1 μm, and the applied film was pre-baked at 100° C. for 3 minutes, and then exposed to a high-pressure mercury lamp. The applied film was then post-baked at 230° C. for 30 minutes to obtain a cured coating film formed only in the solid portion.
The resulting cured coating film of each solid portion was immersed in N-methylpyrrolidone heated to 100° C. and kept warm for 10 minutes in an oven at 100° C. Thereafter, the absorbance of the N-methylpyrrolidone was measured with a spectrophotometer (UV-2500PC), and the maximum peak absorbance was taken as the value of solvent resistance.

It was confirmed that the colored compositions and colored resist compositions according to the examples were excellent in fluidity and stability over time.
Furthermore, the colored resist compositions according to the examples had an OD value of 1.25 or more and solvent resistance of 0.60 or less, and were confirmed to be excellent in light blocking properties and solvent resistance.
Since the colored compositions and colored resist compositions according to the examples have the above-mentioned properties, they can be suitably used as black matrices, black column spacers, or black partition materials for image display devices, touch panels, and the like.
On the other hand, none of the colored compositions and colored resist compositions according to the comparative examples had both excellent light-shielding properties and excellent solvent resistance.

The present invention provides a colored composition that has excellent light-shielding properties and solvent resistance, and a colored resist composition that contains the same.

Claims (3)

Contains a pigment and a binder resin,
The pigment is at least one selected from the group consisting of C.I. Pigment Orange 16 and C.I. Pigment Yellow 139;
C.I. Pigment Blue 60, and
C.I. Pigment Violet 29,
The content of one or more selected from the group consisting of C.I. Pigment Orange 16 and C.I. Pigment Yellow 139 is 5 to 45% by mass based on the total amount of the pigment,
The coloring composition is characterized in that the binder resin has an acid value of 40 to 200 mgKOH/g. A colored resist composition produced using the colored composition according to claim 1. The colored composition according to claim 1, or the colored resist composition according to claim 2, used as a black matrix, black column spacer, or black partition material.