JP2020132776A - Coloring composition, and coloring resist composition containing the same - Google Patents

Abstract

To provide a coloring composition that gives a black resist pattern having excellent light blocking performance, and an extremely good voltage retention, and a coloring resist composition containing the same.SOLUTION: A coloring composition contains a pigment and a binder resin. The pigment contains a pigment shown in the following (A), and C.I. pigment blue 60. (A): One embodiment is a pigment that includes a pigment represented by the following formula, and one or more selected from the group consisting of an isoindoline yellow pigment and a purple pigment.SELECTED DRAWING: None

Description

The present invention relates to a coloring 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 crystals and plasmas, gaps in coloring patterns in the display area of a screen, edges of a peripheral portion of the display area, and TFTs are used. In the liquid crystal display, it is used to provide a light-shielding film (black matrix) on the outside light side of the TFT. Then, in the liquid crystal display, the leakage light mainly from the backlight is prevented, and in the plasma display, 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. It is useful for.

For example, in a color filter used to convert white light from a backlight of a liquid crystal display into colored light, red, green, and blue are usually different 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 hue pixels in a pattern such as a stripe shape or a mosaic shape.

Also, in the touch panel that combines the image display device and the position input device, a color filter in which a black matrix is formed as a light-shielding film is also used, and so far, the cover glass is sandwiched between the touch panel and the sensor substrate. It was generally done to form on the side. However, as the demand for weight reduction of touch panels increases, the development of a technique 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, in Patent Document 1, in a photosensitive coloring composition for forming a color spacer, a specific pigment and carbon black are used in combination as a colorant, and the content ratio of carbon black is set within a specific range to obtain shielding properties and the like. The technology for granting is disclosed.

Further, for example, in Patent Document 2, a technique for maintaining light-shielding property and voltage retention of liquid crystal by appropriately combining pigment types having different light absorption characteristics and ensuring a balance of light absorption in the ultraviolet region and the visible region is used. It is disclosed.

By the way, if the voltage retention rate of a photosensitive composition such as a black matrix constituting the liquid crystal layer of an image display device is low, it causes display unevenness.
In the above-mentioned technique, there is room for improvement in the voltage retention rate, and it is desired to develop a black matrix composition capable of obtaining a black resist pattern having an excellent shielding property and a further excellent voltage retention rate. Was there.

Japanese Unexamined Patent Publication No. 2016-177190 International Publication No. 2013/115268 Pamphlet

Therefore, an object of the present invention is to provide a colored composition capable of obtaining a black resist pattern having excellent light-shielding property and extremely excellent voltage retention, and a colored resist composition containing the same. And.

The present inventors diligently studied the pigment and the binder resin contained in the coloring composition, and found that C.I. I. We have found that by using Pigment Blue 60 and a pigment having a specific structure, it is possible to obtain a coloring composition capable of obtaining a black resist pattern having excellent light-shielding properties and extremely excellent voltage retention. The invention was completed.

〔式（Ａ１）中、Ｘは二重結合を示し、幾何異性体としてそれぞれ独立にＥ体又はＺ体であり、Ｒ^１１は、各々独立に、水素原子、メチル基、ニトロ基、メトキシ基、ブロモ基、クロロ基、フルオロ基、カルボキシ基、又は、スルホ基を示し、Ｒ^１２は、各々独立に、水素原子、メチル基、又はフェニル基を示し、Ｒ^１３は、各々独立に、水素原子、メチル基、又は塩素原子を示す。〕
（Ａ２）イソインドリン系黄色顔料及び紫色顔料に関する。 That is, the present invention contains a pigment and a binder resin, and the pigment is the pigment shown in the following (A) and C.I. I. A coloring composition comprising Pigment Blue 60.
(A) A pigment represented by the following general formula (A1) and a pigment containing one or more selected from the group consisting of the following (A2).

[In formula (A1), X represents a double bond and is independently an E- or Z-form as a geometric isomer, and R ¹¹ is an independently hydrogen atom, methyl group, nitro group, methoxy group, and the like. It represents a bromo group, a chloro group, a fluoro group, a carboxy group, or a sulfo group, R ¹² independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ¹³ independently represents a hydrogen atom, respectively. Indicates a methyl group or a chlorine atom. ]
(A2) Regarding isoindoline-based yellow pigments and purple pigments.

The content of the isoindoline-based yellow pigment including the above (A2) is 8% by mass or more in terms of mass fraction with respect to the total mass of the pigment, and the above C.I. I. The content of Pigment Blue 60 is preferably 10% by mass or more in terms of mass fraction with respect to the total mass of the pigment.
The isoindoline-based yellow pigment is C.I. I. Pigment Yellow 139 and C.I. I. It is preferably one or more selected from the group consisting of Pigment Yellow 185.
In addition, the purple pigment is C.I. I. Pigment Violet 23 and C.I. I. It is preferably one or more selected from the group consisting of pigment violet 29.
In addition, the coloring composition of the present invention may further contain carbon black.
The present invention is also a colored resist composition containing the coloring composition of the present invention.
The coloring composition and coloring resist composition of the present invention are preferably used as a black matrix, a black column spacer, or a black partition material.
Hereinafter, the coloring composition of the present invention and the colored resist composition containing the same will be described in detail.

〔式（Ａ１）中、Ｘは二重結合を示し、幾何異性体としてそれぞれ独立にＥ体又はＺ体であり、Ｒ^１１は、各々独立に、水素原子、メチル基、ニトロ基、メトキシ基、ブロモ基、クロロ基、フルオロ基、カルボキシ基、又は、スルホ基を示し、Ｒ^１２は、各々独立に、水素原子、メチル基、又はフェニル基を示し、Ｒ^１３は、各々独立に、水素原子、メチル基、又は塩素原子を示す。〕
（Ａ２）イソインドリン系黄色顔料及び紫色顔料 (Pigment)
In the coloring composition of the present invention, the pigments are the pigments shown in (A) below and C.I. I. Includes Pigment Blue 60.
By using the above pigment, it is possible to obtain a coloring composition capable of obtaining a black resist pattern having excellent light-shielding property and extremely excellent voltage retention.
(A) A pigment represented by the following general formula (A1) and a pigment containing one or more selected from the group consisting of the following (A2).

[In formula (A1), X represents a double bond and is independently an E- or Z-form as a geometric isomer, and R ¹¹ is an independently hydrogen atom, methyl group, nitro group, methoxy group, and the like. It represents a bromo group, a chloro group, a fluoro group, a carboxy group, or a sulfo group, R ¹² independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ¹³ independently represents a hydrogen atom, respectively. Indicates a methyl group or a chlorine atom. ]
(A2) Isoindoline yellow pigment and purple pigment

The above formula (A1) is an organic black pigment, and C.I. I. When used in combination with Pigment Blue 60, it is possible to impart excellent shielding properties and voltage retention to the black resist pattern obtained by the coloring composition.
In the above formula (A1), from the viewpoint of light-shielding property, all of R ^{11 to} R ¹³ are preferably hydrogen atoms.

C. above. I. From the viewpoint of light-shielding property, the content of Pigment Blue 60 is preferably 5 to 70% by mass, more preferably 8 to 60% by mass, and 10 to 55% by mass with respect to the total mass of the pigment. It is more preferably 15 to 50% by mass, and particularly preferably 15 to 50% by mass.
The content of the pigment represented by the above formula (A1) is preferably 1 to 80% by mass, more preferably 8 to 50% by mass, based on the total mass of the pigment, from the viewpoint of light-shielding property. It is more preferably 10% by mass or more, and particularly preferably 20% by mass or more.

The yellow pigment is an isoindoline-based yellow pigment.
The above-mentioned isoindoline-based yellow pigment and the purple pigment described later were used in C.I. I. When used in combination with Pigment Blue 60, it is possible to impart excellent shielding properties and voltage retention to the black resist pattern obtained by the coloring composition.
From the viewpoint of shielding property and voltage retention, the isoindoline-based yellow pigment has a C.I. I. Pigment Yellow 139, 185 is preferred.

Examples of the purple pigment include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned.
Among them, from the viewpoint of dispersibility and shielding property, C.I. I. Pigment Violet 23, 29 is preferably used, and from the viewpoint of preferably preventing light leakage, C.I. I. Pigment Violet 29 is more preferred.

From the viewpoint of light-shielding property, the content of the isoindoline-based yellow pigment is preferably 5 to 60% by mass, more preferably 8 to 50% by mass, and 10 to 10% by mass with respect to the total mass of the pigment. It is more preferably 45% by mass, and particularly preferably 15% by mass or more.
From the viewpoint of light-shielding property, the content of the purple pigment is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, based on the total mass of the pigment. It is more preferably 15% by mass or more, and particularly preferably 20% by mass or more.

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

The coloring composition of the present invention contains the above (A2) from the viewpoint of preventing light leakage and improving the exposure sensitivity, and the content of the isoindoline-based yellow pigment is the total mass of the pigment of the coloring composition. It is 8% by mass or more in terms of mass fraction with respect to the above C.I. I. The content of Pigment Blue 60 is preferably 10% by mass or more in terms of mass fraction with respect to the total mass of the pigment of the coloring composition.
In the coloring composition of the present invention, the above-mentioned isoindoline-based yellow pigment and the above-mentioned C.I. I. By containing Pigment Blue 60 in a predetermined range, the light transmittance at a wavelength of 440 nm and a wavelength of 510 nm can be lowered in the black resist pattern obtained by using the coloring composition, and the light of the backlight can be reduced. Leakage can be suitably prevented. On the other hand, the transmittance of light at a wavelength of 365 nm can be increased, and the sensitivity during exposure can be improved. In addition, the transmittance of light at a wavelength of 650 nm can be preferably adjusted, and shielding properties and apparent blackness can be preferably imparted.

In the coloring composition of the present invention, the pigment may contain other pigments such as 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 particular limitation as long as it is a resin of a member that can be used for a color filter, and is an alkali-soluble resin, a thermosetting resin, a thermoplastic resin, and a photopolymerizable compound (photopolymerizable resin, non-photopolymerizable resin). Monomers, oligomers, etc. that have one or more saturated bonds in the molecule) and the like can be mentioned. These can be used alone or in combination of two or more.
In the coloring composition of the present invention, the binder resin is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, based on the total solid content.

Examples of the alkali-soluble resin include alkali-soluble copolymers and alkali-soluble cardo resins.
Examples of the alkali-soluble copolymer include carboxyl groups such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, citraconic acid, citraconic anhydride, and citraconic acid monoalkyl ester. Mono (meth) acryllate having saturated monomers and styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol methacrylate, dicyclopentadiene skeleton , N-Phenylmaleimide, a copolymer obtained by reacting at least one selected from the group consisting of polystyrene macromonomer and polymethylmethacrylate macromonomer, and an acid group-introduced epoxy acrylate resin.

Examples of the alkali-soluble cardo resin include an epoxy (meth) acrylate acid adduct having a fluorene skeleton, which is an adduct of a fluorene epoxy (meth) acrylic acid derivative and a dicarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. Can be mentioned.
The alkali-soluble resin can be used alone or in combination of two or more. 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 from the viewpoint of coating film forming property and alkali developing property.
The alkali-soluble resin may be used alone or in combination of two or more, depending on the required performance.

Examples of the thermosetting resin and thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyvinyl acetate. Polyurethane resin, phenol resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, celluloses, polybutadiene, polyimide resin, polyamideimide resin, benzoguanamine resin, melamine Examples include resins and urea resins.

The photopolymerizable resin includes a (meth) acrylic compound and silicic acid via an isocyanate group, an aldehyde group, an epoxy group, or the like in a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group. A resin having a photocrosslinkable group such as the above is used. A linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterled with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified polymer is also used.

In the photopolymerizable compound, examples of the monomer having one photopolymerizable unsaturated bond in the molecule include methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Alkyl methacrylate or acrylate; aralkyl methacrylate or acrylate such as benzyl methacrylate and benzyl acrylate; alkoxy alkyl methacrylate or acrylate such as butoxyethyl methacrylate and butoxyethyl acrylate; N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate and the like. Aminoalkyl methacrylate or acrylate; methacrylic acid ester or acrylic acid ester of polyalkylene glycol alkyl ether such as diethylene glycol ethyl ether, triethylene glycol butyl ether, dipropylene glycol methyl ether; polyalkylene glycol aryl ether such as hexaethylene glycol phenyl ether. Methacrylate or acrylic acid ester; isobonyl methacrylate or acrylate; glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate or acrylate and the like.

In the photopolymerizable compound, examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, and 1,3-butylene glycol dimethacrylate. , Diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylpropantrimethacrylate, pentaerythritol 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 di. Acrylate, Polyethylene Glycol Diacrylate, Polypropylene Glycol Diacrylate, Tetraethylene Glycol Diacrylate, Trimethylol Propanetriacrylate, Pentaerythritol Triacrylate, Pentaerythritol Tetraacrylate, Dipentaerythritol Tetraacrylate, Dipentaerythritol Hexaacrylate, Dipentaerythritol Penta Examples include acrylate.

(Carbon black)
The coloring composition of the present invention may contain carbon black from the viewpoint of adjusting the color.
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 manufactured by Mitsubishi Chemical Corporation, SpecialBlack350, SpecialBlack250, SpecialBlack550, NEROX2500, NEROX3500, NEROX305, etc. manufactured by Orion Engineered Carbons. MOGUL L, REGAL400R, TPK1101R, TPK1104R, TPK1227R, etc. manufactured by Cabot Corporation, RAVEN1200, RAVEN1250, RAVEN1255, RAVEN1190U, RAVEN1170, RAVEN1035, RAVEN1080U, RAVEN1060U, etc.
Among them, acidic carbon black having a pH of 5 or less and having an acidic group such as a carboxyl group is preferable. Further, those having a particle size of 20 to 60 nm are preferable.
Examples of the acidic carbon black satisfying the above include NEROX2500, NEROX3500, TPK1101R, TPK1104R, TPK1227R and the like.
The particle size means the average primary particle size measured or calculated by microscopic observation.

The content of the acidic carbon black is not particularly limited, but is preferably 70% by mass or less with respect to the mass of the total pigment of the coloring composition of the present invention, for example. If the amount of the acidic carbon black exceeds 70% by mass, the voltage holding ratio may be lowered and the exposure sensitivity may be lowered.
A more preferable upper limit of the content of the acidic carbon black is 30% by mass with respect to the mass of the total pigment of the coloring composition of the present invention.
The coloring composition of the present invention does not have to contain the above-mentioned acidic carbon black.

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

(Pigment dispersant)
The coloring composition of the present invention preferably contains a pigment dispersant.
The pigment dispersant includes a basic group-containing pigment dispersant, an anionic surfactant, a basic group-containing polyester pigment dispersant, a basic group-containing acrylic pigment dispersant, and a basic group-containing urethane pigment. Dispersants, basic group-containing carbodiimide pigment dispersants, acidic group-containing polymer pigment dispersants and the like can be used.
These basic group-containing pigment dispersants may be used alone or in combination of two or more. Of these, a basic group-containing polymer pigment dispersant is preferable from the viewpoint of obtaining good pigment dispersibility.

Specific examples of the basic group-containing polymer pigment dispersant include
(1) From polyesters, polyamides and polyesteramides having an amino group and / or imino group of a polyamine compound (for example, poly (lower alkyleneamine) such as polyallylamine, polyvinylamine, polyethylene polyimine) and a free carboxyl group. (Japanese Patent Laid-Open No. 2001-59906), a reaction product with at least one selected from the above group.
(2) Reaction product of a low molecular weight amino compound such as poly (lower) alkyleneimine or methyliminobispropylamine and a polyester having a free carboxyl group (Japanese Patent Laid-Open No. 54-37082, Japanese Patent Application Laid-Open No. 01-31177) Issue),
(3) Polyisocyanate compounds such as alcohols such as methoxypolyisocyanate glycol and polyesters having one hydroxyl group such as caprolactone polyester, compounds having 2 to 3 isocyanate group reactive functional groups, and isocyanate group reactive. A reaction product obtained by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound having a functional group and a tertiary amino group (Japanese Patent Laid-Open No. 02-612).
(4) A compound obtained by reacting a polyisocyanate compound with a hydrocarbon compound having an amino group with a polymer of an acrylate having an alcoholic hydroxyl 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 (Japanese Patent Laid-Open No. 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 (Japanese Patent Laid-Open No. 09-87537).
(8) A reaction product of a polycarbonate compound having a functional group capable of reacting with an amino group at one end and a polyamine compound (Japanese Patent Laid-Open No. 09-194585).
(9) Selected from methacrylic 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, or acrylic acid esters. At least one of the basic group-containing polymerization monomers such as acrylamide, methacrylicamide, N-methylolamide, vinyl imidazole, vinylpyridine, and a monomer having an amino group and a polycaprolactone skeleton, and styrene, a styrene derivative, Copolymer with at least one of other polymerizable monomers (Japanese Unexamined Patent Publication No. 01-164429),
(10) Basic group-containing carbodiimide pigment dispersant (International Publication WO04 / 00950),
(11) A block copolymer composed of a block having a basic group such as a tertiary amino group and a quaternary ammonium salt machine and a block having no functional group (see the description of JP-A-2005-55514).
(12) A pigment dispersant obtained by carrying out a Michael addition reaction of a polycarbonate compound with polyallylamine (Japanese Patent Laid-Open No. 09-194585).
(13) A carbodiimide compound having at least one polybutadiene chain and at least one basic nitrogen-containing group (Japanese Patent Laid-Open No. 2006-257243).
(14) Examples thereof include a carbodiimide compound having at least one side chain having an amide group in the molecule and at least one basic nitrogen-containing group (Japanese Patent Laid-Open No. 2006-176657).
(15) A polyurethane compound having a structural unit having an ethylene oxide chain and a propylene oxide chain and having an amino group quaternized by a quaternizing agent (Japanese Patent Laid-Open No. 2009-175613).
(16) Obtained by reacting the isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule with the active hydrogen group of a compound having an active hydrogen group in the molecule and having a carbazole ring and / or an azobenzene skeleton. The carbazole ring with respect to the total of the isocyanate group derived from the isocyanate compound having an isocyanurate ring in the molecule of the compound, and the urethane bond and urea bond generated by the reaction of the isocyanate group and the active hydrogen group. And compounds in which the number of azobenzene skeletons is 15-85% (Japanese Patent Application No. 2009-220836).
(17) A graft copolymer in which a polyether or a polyester side chain is introduced into an acrylate polymer having an amino group.

Among the above basic group-containing polymer pigment dispersants, the basic group-containing urethane polymer pigment dispersant, the basic group-containing polyester polymer pigment dispersant, and the basic group-containing acrylic polymer pigment dispersant are more suitable. Amino group-containing urethane-based polymer pigment dispersant, amino group-containing polyester-based polymer pigment dispersant, and amino group-containing acrylic polymer pigment dispersant are more preferable. Among the above basic group-containing polymer pigment dispersants, a basic group (amino group) -containing polymer pigment dispersant having at least one selected from the group consisting of polyester chains, polyether chains, and polycarbonate chains is particularly preferable. preferable.

In the coloring composition of the present invention, 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 pigment.

〔式中、Ｙ及びＺ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 is a pigment dispersion aid represented by the following general formulas (1) and / or (2), and / or a pigment dispersion which is a sulfonated copper phthalocyanine (which may be neutralized). Auxiliary agent and / or C.I. I. It preferably contains a pigment dispersion aid which is a sulfonated (may be neutralized) of Pigment Yellow 138.

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

The pigment dispersion aid is used to disperse the pigment.
By using the pigment dispersion aid and the pigment dispersant in combination when dispersing the pigment, excellent fluidity and stability over time can be obtained. Further, when the coloring composition is used as a black matrix, a black column spacer, or a coloring resist composition for a black partition material, it is possible to obtain a high optical density.

In the above general formulas (1) and (2), Y and Z represent the same or different phenyl groups 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 .
Regarding "NR ¹ R ² R ³ R ⁴ " (M) of the above general formulas (1) and (2), R ¹ , R ² , R ³ and R ⁴ are the same or different and are substituted with other substituents. It represents a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be used, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with another substituent. Here, the saturated or unsaturated aliphatic hydrocarbon group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group and a hexyl group. , Alkyl groups such as octyl group and decyl group; alkenyl groups such as vinyl group, allyl group and 1-butenyl group; alkynyl groups such as ethynyl group and propynyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of the other substituent include a hydroxyl group, a halogen, a carboxyl group, an amino group, a lower alkyl group (1 to 5 carbon atoms) and the like.
It should be noted that ^one of R ¹ , R ² , R ³ and R ⁴ may be substituted with another substituent, or two or more may be substituted with another substituent.
Further, "m" in the general formulas (1) and (2) is an integer of 1 or more.

Among the above compounds (pigment dispersion aids), the compound represented by the general formula (1) is an enol type compound, and the compound represented by the general formula (2) is a keto type tautomer. Auxiliary agents include both compounds. That is, the pigment dispersion aid includes both the compound represented by the general formula (1) or (2) and the compound represented by the general formulas (1) and (2). Any of the above is included.

Such a pigment dispersion aid is a novel compound. For example, the monoazo compounds of the following formulas (3) to (30) are dissolved in concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or a mixture thereof at room temperature or higher. The suspension obtained by heating to 80 to 90 ° C. and then diluted with a large amount of water can be filtered, washed with water, and the obtained filter cake can be dried and crushed to produce a commercially available product. ..

Among these pigment dispersion aids, Y of the above general formulas (1) and / or (2) is a 2,5-dichlorophenyl group from the viewpoint of being able to impart good fluidity and stability over time. A compound represented by the following general formula (31) in which Z is a phenyl group (a compound obtained by the above production method using the monoazo compound of the above formula (3): enol type) and / or the following general formula (32). A compound represented by the above (a compound obtained by the above-mentioned production method or the like using the monoazo compound of the above-mentioned formula (4): keto-type) is suitable.

In the coloring composition of the present invention, the pigment dispersion aid is preferably 30 parts by mass or less, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the pigment.
The pigment dispersion aid may not improve the pigment dispersion effect even if it exceeds 30 parts by mass with respect to 100 parts by mass of the pigment.

(Organic solvent)
The coloring composition of the present invention preferably contains an organic solvent.
As the organic solvent, the 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 70 to 300 ° C. at normal pressure (1.013 × 10 ² kPa). , Aromatic hydrocarbon-based organic solvent, nitrogen-containing organic solvent and the like are preferable.

Specific examples of such a 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. Ether-based organic solvents such as monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl Ether ester organic solvents such as ether acetate and propylene glycol monoethyl ether acetate, ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone and δ-butyrolactone, methyl 2-hydroxypropionate, 2-hydroxypropion Ethyl acid, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ester-based organic solvents such as ethyl propionate, ethyl ethoxyacetate, hydroxyacetate, n-amyl formate, nitrogen-containing organic solvents such as N-methylpyridone, N, N-dimethylformamide, N, N-dimethylacetamide, etc. These organic solvents can be used alone or in admixture of two or more.

Among these organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and cyclohexanone are used in terms of boiling point, solubility, dispersibility, coatability, etc. , 2-Heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl acrylate and the like, preferably propylene glycol monomethyl ether. Acetate is more preferred.

(Other additives)
Depending on the method for producing the coloring 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 for example, benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxy. Acetphenone, 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-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, triazine-based photopolymerization initiator, oxime An ester-based photopolymerization initiator or the like can be used. These photopolymerization initiators can be used alone or in combination of two or more.

<Manufacturing method of coloring composition>
An example of a method for producing a coloring composition using the above materials will be described.
If necessary, binder resin, carbon black, pigment dispersant, pigment dispersion aid, organic solvent and other additives are added to and mixed with each of the above pigments to obtain a mixture.
The obtained mixture is kneaded and dispersed using various dispersers such as a roll mill, a kneader, a high-speed stirrer, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser, and a pigment dispersion composition of each color is prepared. To get.
Next, the obtained pigment dispersion compositions of each color are blended so as to be pseudo-blackened, a binder resin, an organic solvent, and other additives are added as necessary, and a stirring device such as a high-speed stirrer is used. After uniformly mixing, the mixture is filtered through a filter to obtain the coloring composition of the present invention. In the above production method, the binder resin can be added at the time of producing the pigment dispersion composition. Further, after the pigment dispersion composition is prepared, it can be added at the time of preparation of the coloring composition.

(Covariance)
A mixture consisting of a mixed pigment in which each pigment is blended so as to be pseudo-blackening, a pigment dispersant, a pigment dispersion aid, an organic solvent, a binder resin if necessary, and other additives if necessary is obtained. The obtained mixture is kneaded and dispersed using various dispersers such as a roll mill, a kneader, a high-speed stirrer, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser to obtain a pigment dispersion composition. ..
Next, a binder resin, an organic solvent, and other additives were added to the obtained pigment dispersion composition as needed, mixed uniformly using a stirring device such as a high-speed stirrer, and then filtered through a filter. Obtain the coloring composition of the present invention. In the above production method, the binder resin can be added at the time of producing the pigment dispersion composition.
Further, after the pigment dispersion composition is prepared, it can be added at the time of preparation of the coloring composition.

The coloring 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 viscosity is the viscosity measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) after sealing the coloring composition of the present invention in a glass bottle or the like and storing it for one day.

The coloring composition of the present invention preferably has a stability over time of 0.8 to 1.1.
If the stability over time is less than 0.8 or more than 1.1, the coatability and developability may be adversely affected.
Regarding the stability over time, the viscosity at 25 ° C. after the coloring composition of the present invention is sealed in a glass bottle or the like and stored at room temperature (25 ° C.) for 1 day and the coloring composition of the present invention are sealed in a glass bottle or the like. Then, the viscosity at 25 ° C. after storage at 40 ° C. for 7 days was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), and (viscosity after storage at 40 ° C. for 7 days) / (at room temperature). It was determined as the viscosity after storage for 1 day).

Next, an example of using the coloring composition of the present invention 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 composed of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an organic solvent, and various additions such as a polymerization inhibitor, if necessary, in addition to the coloring composition of the present invention. Those obtained by appropriately adding an agent are preferable.

<Constituent material 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 coloring composition of the present invention is preferably 20 to 95% by mass, preferably 30 to 90% by mass, based on the total solid content of the colored resist composition of the present invention. More preferred.

(Pigment dispersant)
As the pigment dispersant, those described in the coloring composition of the present invention can be preferably used.
In the colored resist composition of the present invention, the content of the pigment dispersant is preferably 0.1 to 50 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all the pigments used.

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

(Photopolymerization initiator)
The photopolymerization initiator is not particularly limited, but is, for example, benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxy. Acetphenone, 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-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, triazine-based photopolymerization initiator, oxime An ester-based photopolymerization initiator or the like can be used. These photopolymerization initiators can be used alone or in combination of two or more.
In the coloring composition of the present invention, the photopolymerization initiator is preferably 0.1 to 10% by mass, preferably 0.5 to 6% by mass, based on the total solid content. More preferred.

(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 from the viewpoint of polymerizable property, crosslinkability and the like. These photopolymerizable monomers can be used alone or in combination of two or more.

(Organic solvent)
As the organic solvent, those described in the coloring composition of the present invention can be preferably used.
In the colored resist composition of the present invention, the content of the organic solvent is 5 to 90 mass by mass with respect to the total amount of the colored resist composition of the present invention from the viewpoint of solubility, pigment dispersibility, coatability, etc. of each material. It is preferably%.

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

<Method for Producing Colored Resist Composition of the Present Invention>
The method for producing a colored resist composition of the present invention is an example of a preferred embodiment of the present invention, and the present invention is not limited thereto.
For example, a method of adding a binder resin, a photopolymerizable compound, a photopolymerization initiator, an organic solvent, and other additives to the coloring composition of the present invention and stirring and mixing using a stirrer or the like can be used.

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 viscosity is the viscosity measured using a BE type viscometer (manufactured by Toki Sangyo Co., Ltd.) after the colored resist composition of the present invention is sealed in a glass bottle or the like and stored for 1 day.

The colored resist composition of the present invention preferably has a stability over time of 0.8 to 1.2.
If the stability over time is less than 0.8 or more than 1.2, the coatability and developability may be adversely affected. The stability over time is determined by 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 colored composition of the present invention is placed in a light-shielding glass bottle. The viscosity at 25 ° C. after being stored at a low temperature (5 ° C.) for 7 days was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), and stored at a low temperature (5 ° C.) for 7 days. Viscosity) / (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, more preferably 1.20 or more when a resist pattern having a thickness of 1 μm is formed.
When the optical density (OD value) is 1.25 or more, it can be said that the shielding property is sufficient.
For the optical density (OD value), a resist pattern of only a solid portion of 1 μm was formed using the colored resist composition of the present invention, and a Macbeth densitometer (TD-931, trade name, manufactured by Macbeth) was used. It is a measured value.

In the colored resist composition of the present invention, the light transmittance at a wavelength of 440 nm and a wavelength of 510 nm when a resist pattern having a thickness of 1 μm is formed is preferably 5% or less, and more preferably 3% or less.
When the light transmittance at the wavelengths of 440 nm and 510 nm is 5% or less, light leakage can be sufficiently prevented and contrast can be preferably imparted.
Further, in the colored resist composition of the present invention, the light transmittance at a wavelength of 365 nm when a resist pattern having a thickness of 1 μm is formed is preferably 1% or more, and more preferably 5% or more.
When the light transmittance at the wavelength of 365 nm is 5% or more, the exposure sensitivity can be improved.
Further, the colored resist composition of the present invention preferably has a light transmittance of 55% or less at a wavelength of 650 nm when a resist pattern having a thickness of 1 μm is formed, preferably 40%, from the viewpoint of preferably imparting shielding properties. The following is more preferable.
The transmittance is measured by forming a resist pattern of only a solid portion having a thickness of 1 μm on a glass substrate using a colored resist composition and measuring it with a spectrophotometer (UV-2500PC, manufactured by Shimadzu Corporation). , It is a value converted into a transmittance.

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

According to the present invention, it is possible to provide a colored composition capable of obtaining a black resist pattern having excellent light-shielding property and extremely excellent voltage retention, and a colored resist composition containing the same.

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.

チタンブラック（三菱マテリアル電子化成社製、製品名１３Ｍ−Ｔ）
＜カーボンブラック＞
ＴＰＫ１１０４Ｒ（キャボット製、吸油量：３８ｍｌ／１００ｇ、ｐＨ：２．７）
＜バインダー樹脂＞
ＢｚＭＡ／ＭＡＡ（アルカリ可溶性樹脂、ベンジルメタクリレート／メタクリル酸共重合体、理論酸価：１２０ｍｇＫＯＨ／ｇ、質量平均分子量：１００００）
＜顔料分散剤＞
ＢＹＫ−ＬＰＮ−２２１０２（ビックケミー社製、顔料親和性基を有するセグメントとバインダー相溶性基を有するセグメントとからなるアクリル系ブロック共重合体）
＜顔料分散助剤＞
１００ｍｌ三角フラスコに濃硫酸を３０ｍｌ仕込み、マグネチックスターラーで攪拌しながらピグメントレッド２（上記式（３）及び／又は（４）で表される化合物）を１０ｇ投入し、室温で３０分攪拌した。１Ｌビーカーに水５０ｇと氷５０ｇの混合物を入れ、上記の反応物をこの氷水中に注ぎ、マグネチックスターラーで３０分攪拌した。これを減圧下で濾過・水洗し、得られた固体を乾燥させて、顔料分散助剤１（上記一般式（３１）及び／又は（３２）で表される化合物：Ｍ＝Ｈ）１２ｇを得た。
＜有機溶剤＞
ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート） The materials of the coloring composition used in the following examples and comparative examples are as follows.
<Pigment>
P. V. 23 (CI Pigment Violet 23)
P. V. 29 (CI Pigment Violet 29)
P. V. 32 (CI Pigment Violet 32)
P. R. 254 (CI Pigment Red 254)
P. Y. 139 (CI Pigment Yellow 139)
P. Y. 155 (CI Pigment Yellow 155)
P. Y. 180 (CI Pigment Yellow 180)
P. Y. 185 (CI Pigment Yellow 185)
P. B. 60 (CI Pigment Blue 60)
P. B. 15: 3 (CI Pigment Blue 15: 3)
P. B. 15: 6 (CI Pigment Blue 15: 6)
P. O. 64 (CI Pigment Orange 64) Lactam Black: manufactured by BASF, Irgaphor (registered trademark) Black S 0100 CF (pigment represented by the following general formula)

Titanium Black (manufactured by Mitsubishi Materials Electronics Chemicals, Inc., product name 13MT)
<Carbon black>
TPK1104R (manufactured by Cabot, oil absorption: 38 ml / 100 g, pH: 2.7)
<Binder resin>
BzMA / MAA (alkali-soluble resin, benzyl methacrylate / methacrylic acid copolymer, theoretical acid value: 120 mgKOH / g, mass average molecular weight: 10000)
<Pigment dispersant>
BYK-LPN-22102 (Acrylic block copolymer manufactured by Big Chemie, consisting of a segment having a pigment affinity group and a segment having a binder compatible group)
<Pigment dispersion aid>
30 ml of concentrated sulfuric acid was charged in a 100 ml Erlenmeyer flask, 10 g of Pigment Red 2 (compound represented by the above formulas (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 was poured into the ice water and stirred with a magnetic stirrer for 30 minutes. This is filtered and washed with water under reduced pressure, and the obtained solid is dried to obtain 12 g of a pigment dispersion aid 1 (compound represented by the above general formulas (31) and / or (32): M = H). It was.
<Organic solvent>
PGMEA (Propylene Glycol Monomethyl Ether Acetate)

The materials of the black matrix, the black column spacer, or the colored resist composition for the black partition material used in the following examples and comparative examples are as follows.
<Binder resin>
SPC-3500 (alkali-soluble resin, theoretical acid value: 60 mgKOH / g, mass average molecular weight: 11000)
<Photopolymerization initiator>
Irgacure 907 (BASF, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one) and Irgacure OXE02 (BASF, Etanon, 1- [9-ethyl-6-] (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime)) 1: 1 (mass ratio) mixture <photopolymerizable monomer>
DPEHA (photopolymerizable compound, dipentaerythritol hexaacrylate)
<Organic solvent>
PGMEA (Propylene Glycol Monomethyl Ether Acetate)

<Preparation of coloring compositions of Examples 1-10 and 21-24, Comparative Examples 1-8 and 17-19>
Various materials were mixed so as to have the compositions shown in Tables 1 and 3 (the amount of each material used in Tables 1 and 3 is mass%), and the meat was kneaded with a bead mill for 24 hours, and Examples 1 to 10 and 21 to 24, The coloring compositions of Comparative Examples 1 to 8 and 17 to 19 were prepared.

<Preparation of colored resist compositions of Examples 11-20 and 25-28, Comparative Examples 9-16 and 20-22>
Using a high-speed stirrer, the colored compositions of Examples 1 to 10 and 21 to 24, Comparative Examples 1 to 8 and 17 to 19 and the other materials were mixed with the compositions of Tables 2 and 4 (each material in Tables 2 and 4). The colored resist compositions of Examples 11 to 20 and 25 to 28 and Comparative Examples 9 to 16 and 20 to 22 are uniformly mixed so as to be used in an amount of (% by mass), and then filtered through a filter having a pore size of 1 μm. I got something.

(Evaluation test)
Obtained in Examples 1-10 and 21-24, the coloring compositions obtained in Comparative Examples 1-8 and 17-19, and Examples 11-20 and 25-28, Comparative Examples 9-16 and 20-22. The fluidity and stability over time of the obtained colored resist composition were evaluated by the following methods, and the results are shown in Tables 1 to 4.
Further, the colored resist compositions obtained in Examples 11 to 20 and Comparative Examples 9 to 16 were applied to form a resist pattern having a thickness of 1 μm, the optical density and voltage retention rate thereof were evaluated, and the results are shown in the table. Shown in 2.
Further, the colored resist compositions obtained in Examples 25 to 28 and Comparative Examples 20 to 22 are applied to form a resist pattern having a thickness of 1 μm, and the optical density and voltage retention rate thereof are evaluated to evaluate wavelengths 365 and 440. The light transmittances at 510 and 650 were measured and the results are shown in Table 4.

<Liquidity>
The colored compositions obtained in Examples 1 to 10 and 21 to 24 and Comparative Examples 1 to 8 and 17 to 19 were taken in glass bottles, sealed tightly, and stored at room temperature (25 ° C.) for 1 day, and then E-type viscosity. The viscosity [mPa · s] at 25 ° C. was measured using a meter (manufactured by Toki Sangyo Co., Ltd.) to evaluate the fluidity.
The colored resist compositions obtained in Examples 11 to 20 and 25 to 28 and Comparative Examples 9 to 16 and 20 to 22, respectively, were taken in a light-shielding glass bottle, sealed tightly, and stored at a low temperature (5 ° C.) for 1 day. , E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity [mPa · s] at 25 ° C. to evaluate the fluidity.

<Stability over time>
The coloring compositions obtained in Examples 1 to 10 and 21 to 24 and Comparative Examples 1 to 8 and 17 to 19 were taken in glass bottles, respectively, and the coloring composition of the present invention was sealed in a glass bottle or the like at room temperature (25 ° C.). ), The viscosity at 25 ° C. after storing for 1 day and the viscosity at 25 ° C. after storing the coloring composition of the present invention in a glass bottle or the like for 7 days at 40 ° C. are measured by an E-type viscometer (Toki Sangyo). It was measured using (manufactured by the same company) and determined as (viscosity after storage at 40 ° C. for 7 days) / (viscosity after storage at room temperature for 1 day).
Further, the colored resist compositions obtained in Examples 11 to 20 and 25 to 28 and Comparative Examples 9 to 16 and 20 to 22 were sealed in a light-shielding glass bottle or the like and stored at a low temperature (5 ° C.) for 1 day. Use an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) to measure the viscosity at 25 ° C. and the viscosity at 25 ° C. after sealing the coloring composition of the present invention in a light-shielding glass bottle or the like and storing it at a low temperature (5 ° C.) for 7 days. It was measured using and determined as (viscosity after storage at 5 ° C. for 7 days) / (viscosity after storage at 5 ° C. for 1 day).

<Optical density (OD value)>
The colored resist compositions of Examples 11 to 20 and 25 to 28 and Comparative Examples 9 to 16 and 20 to 22 were applied onto a glass substrate with a spin coater so as to have a film thickness of 1 μm, and prebaked at 100 ° C. for 3 minutes. After that, it was exposed with a high-pressure mercury lamp and further post-baked at 230 ° C. for 30 minutes to obtain a black resist pattern formed only in the solid portion. The optical density (OD value) of the black resist pattern of each solid portion obtained was measured with a Macbeth densitometer (TD-931, trade name, manufactured by Macbeth).

<Voltage retention rate>
A soda glass substrate having a SiO ₂ film for preventing the elution of sodium ions and having an ITO (indium-tin oxide alloy) electrode vapor-deposited in a predetermined shape was prepared on the surface.
The colored resist compositions of Examples 11 to 20 and 25 to 28 and Comparative Examples 9 to 16 and 20 to 22 are applied onto the soda glass substrate using a spin coater, and then in a clean oven at 90 ° C. 3 Pre-baking was performed for 1 minute to form a coating film having a film thickness of 3.0 μm.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 500 J / m ² without using a photomask.
Then, this substrate is immersed in a developing solution consisting of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C., developed, washed with ultrapure water, air-dried, and post-baked at 230 ° C. for 30 minutes. , The coating film was cured to form a black cured film (black resist pattern) on the substrate.
Next, the liquid crystal cell produced using the above black resist pattern is placed in a constant temperature layer at 60 ° C., and the voltage retention of the liquid crystal cell is measured by the liquid crystal voltage retention measurement system VHR-1A (trade name) manufactured by Toyo Corporation. did. The applied voltage at this time is a square wave of 5.0 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 ms / voltage applied at 0 ms).

<Transmittance>
The colored resist compositions of Examples 25 to 28 and Comparative Examples 20 to 22 were applied onto a glass substrate with a spin coater so as to have a film thickness of 1 μm, prebaked at 100 ° C. for 3 minutes, and then exposed with a high-pressure mercury lamp. Further, post-baking was performed at 230 ° C. for 30 minutes to obtain a black resist pattern formed only in the solid portion.
The absorbance of the obtained solid black resist pattern was measured with a spectrophotometer (UV-2500PC, manufactured by Shimadzu Corporation) and converted into transmittance.

It was confirmed that the colored composition and the colored resist composition according to the examples were excellent in fluidity and stability over time.
Further, it was confirmed that the colored resist composition according to the examples had an OD value of 1.20 or more and a voltage retention rate of 80% or more, and was excellent in light-shielding property and voltage retention rate.
Furthermore, isoindoline-based yellow pigment and C.I. I. The colored resist compositions according to Examples 25 to 28 using Pigment Blue 60 at a specific content have a light transmittance of 5% or less at a wavelength of 440 nm and a wavelength of 510 nm, and a light transmittance at a wavelength of 365 nm. It was confirmed that the content was 10% or more, that light leakage could be suitably prevented, and that the exposure sensitivity was also excellent.
On the other hand, none of the colored composition and the colored resist composition according to the comparative example had excellent light-shielding properties and also excellent voltage retention.
In addition, none of the colored resist compositions according to the comparative examples can prevent light leakage and have excellent exposure sensitivity.

According to the present invention, it is possible to provide a colored composition capable of obtaining a black resist pattern having excellent light-shielding property and extremely excellent voltage retention, and a colored resist composition containing the same.
The coloring composition and coloring resist composition of the present invention can be suitably used as a black matrix, a black column spacer, or a black partition material. It can also be used as a black partition material for OLED displays and organic EL displays.

Claims (7)

Contains pigments and binder resins
The pigments are the pigments shown in (A) below and C.I. I. A coloring composition comprising Pigment Blue 60.
(A) A pigment represented by the following general formula (A1) and a pigment containing one or more selected from the group consisting of the following (A2).

[In formula (A1), X represents a double bond and is independently an E- or Z-form as a geometric isomer, and R ¹¹ is an independently hydrogen atom, methyl group, nitro group, methoxy group, and the like. It represents a bromo group, a chloro group, a fluoro group, a carboxy group, or a sulfo group, R ¹² independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ¹³ independently represents a hydrogen atom, respectively. Indicates a methyl group or a chlorine atom. ]
(A2) Isoindoline yellow pigment and purple pigment The content of the isoindoline-based yellow pigment containing (A2) is 8% by mass or more in terms of mass fraction with respect to the total mass of the pigment. I. The coloring composition according to claim 1, wherein the content of Pigment Blue 60 is 10% by mass or more in terms of mass fraction with respect to the total mass of the pigment. The isoindoline-based yellow pigment is C.I. I. Pigment Yellow 139 and C.I. I. The coloring composition according to claim 1 or 2, which is one or more selected from the group consisting of Pigment Yellow 185. The purple pigment is C.I. I. Pigment Violet 23 and C.I. I. The coloring composition according to any one of claims 1 to 3, which is one or more selected from the group consisting of pigment violet 29. The coloring composition according to any one of claims 1 to 4, further comprising carbon black. A colored resist composition containing the coloring composition according to any one of claims 1 to 5. The colored composition according to any one of claims 1 to 5, or the colored resist composition according to claim 6, which is used as a black matrix, a black column spacer, or a black partition material.