KR20200102356A - Coloring composition and coloring resist composition - Google Patents

Abstract

The present invention provides a coloring composition capable of obtaining a black resist pattern having excellent light-shielding properties and solvent resistance, and a coloring resist composition containing the same. The coloring composition contains a pigment and a binder resin, wherein the pigment includes at least one selected from a group consisting of C.I. pigment orange 16 and C.I. pigment yellow 139, and C.I. pigment blue 60.

Description

A colored composition and a colored resist composition TECHNICAL FIELD [COLORING COMPOSITION AND COLORING RESIST COMPOSITION}

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

Recently, the use of the colored composition for black matrices has been widespread. For example, in a flat panel display such as liquid crystal or plasma, the gap of the colored pattern in the display area of the screen or the edge of the peripheral portion of the display area, and in the liquid crystal display using TFT, TFT It is used to provide a light-shielding film (black matrix) on the external light side of In addition, in a liquid crystal display, it is helpful to improve display characteristics (contrast and color purity) by preventing the leakage of light from the backlight mainly from the backlight, and from spreading mainly due to the cloudiness of each color light in the plasma display.

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

Also, in a touch panel in which an image display device and a position input device are combined, a color filter in which a black matrix is formed as a light-shielding film is similarly used, and so far, it has generally been formed on the side opposite to the sensor substrate with a cover glass interposed therebetween. However, as the demand for weight reduction of the touch panel increases, the development of a technology for simultaneously forming a light shielding film and a touch sensor on the same side of the cover glass is in progress in order to further reduce the weight.

For example, Patent Document 1 discloses a technique for imparting shielding properties, etc. by using a combination of a specific pigment and carbon black as a colorant as a colorant in a photosensitive coloring composition for forming a color spacer and setting the content ratio of carbon black to a specific range. Has been.

Further, for example, Patent Document 2 discloses a technique of maintaining a light shielding property and a voltage retention rate of a liquid crystal by appropriately combining pigment species having different light absorption characteristics to ensure a balance of light absorption in the ultraviolet region and the visible region.

However, when the solvent resistance of a colored composition such as a black matrix constituting a liquid crystal layer of an image display device is low, a problem arises that cracks or omissions occur in the pixel pattern or the colored component is eluted from the pixel pattern.

In the above-described technique, solvent resistance was not examined, and development of a colored composition for a black matrix capable of obtaining a black resist pattern excellent in solvent resistance was required.

Patent Document 1: Japanese Laid-Open Patent No. 2016-177190 Patent Document 2: International Publication No. 2013/115268 pamphlet

Accordingly, an object of the present invention is to provide a colored composition capable of obtaining a black resist pattern having excellent light shielding properties and excellent solvent resistance, and a colored resist composition containing the same.

The present inventors completed the present invention by discovering that in a coloring composition containing a pigment and a binder resin, a colored composition capable of producing a black resist pattern having excellent shielding properties and excellent solvent resistance can be obtained by using a specific pigment in combination. I came to tell you.

That is, the present invention includes a pigment and a binder resin, and the pigment is C.I. Pigment Orange 16 and C.I. At least one selected from the group consisting of Pigment Yellow 139, and C.I. It relates to a coloring composition for a black matrix comprising Pigment Blue 60.

In addition, the pigment is C.I. Pigment Violet 23 and C.I. It is preferable to further include at least one selected from the group consisting of pigment violet 29.

In addition, the present invention is also a colored resist composition produced by using the colored composition of the present invention.

Moreover, it is also the colored composition of this invention, or the colored resist composition of this invention used as a black matrix, a black column spacer, or a black partition material.

Advantageous Effects of Invention According to the present invention, it is possible to provide a colored composition having excellent light-shielding properties and excellent solvent resistance, and a colored resist composition containing the same.

Hereinafter, the colored composition of the present invention and the colored resist composition containing the same will be described in detail.

(Pigment)

In the coloring composition of the present invention, the pigment is C.I. Pigment Orange 16 and C.I. At least one selected from the group consisting of Pigment Yellow 139 and C.I. Includes Pigment Blue 60.

By using the said pigment, it can be set as the coloring composition for black matrices which can obtain a black resist pattern excellent in light-shielding property and also excellent in solvent resistance. From the viewpoint of imparting solvent resistance, the pigment is C.I. Pigment Yellow 139 and C.I. It is preferred to include Pigment Blue 60.

C.I. Pigment Orange 16 and C.I. The content of at least one pigment selected from the group consisting of Pigment Yellow 139 is preferably 5 to 60% by mass, more preferably 8 to 50% by mass, and more preferably 10 to 45% by mass with respect to the total amount of the pigment from the viewpoint of light-shielding property. It is more preferable that it is mass %, and it is especially preferable that it is 10-40 mass %.

C.I. The content of Pigment Blue 60 is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, still more preferably 15 to 55% by mass, with respect to the total mass of the pigment from the viewpoint of light blocking, It is particularly preferable that it is 20-50 mass %.

The pigment is C.I. Pigment Violet 23 and C.I. It is preferable to further include at least one selected from the group consisting of pigment violet 29.

The pigment is C.I. Pigment Violet 23 and C.I. By further including at least one selected from the group consisting of pigment violet 29, excellent shielding properties can be imparted to the black resist pattern obtained by the colored composition.

From the viewpoint of imparting solvent resistance, the pigment is C.I. It is more preferable to include pigment violet 29.

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

In the coloring composition of the present invention, the pigment is preferably 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 pigment may contain other pigments such as carbon black, red pigment, orange (orange) pigment, blue pigment, and green pigment as long as the effect of the present invention is not impaired.

(Binder resin)

The colored composition of the present invention contains a binder resin.

As the binder resin, any resin that can be used for a color filter can be used without particular limitation, and alkali-soluble resin, thermosetting resin, thermoplastic resin, photopolymerizable compound (photopolymerizable resin, photopolymerizable unsaturated bond having at least one Monomer, oligomer, etc.), etc. are mentioned. These can be used alone or in combination of two or more.

In the colored composition of the present invention, the binder resin is preferably 1 to 40% by mass, more preferably 3 to 25% 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 unsaturated monomers containing 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, Styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol methacrylate, dicyclopenta It is a copolymer and epoxy acrylate resin obtained by reacting at least one selected from the group consisting of mono(meth)acrylate, N-phenylmaleimide, polystyrene macromonomer, and polymethylmethacrylate macromonomer having a diene skeleton.

Examples of the alkali-soluble cardo resin include an epoxy (meth)acrylate acid adduct having a fluorene skeleton, which is an addition product of a fluorene epoxy (meth)acrylic acid derivative and a dicarboxylic anhydride and/or tetracarboxylic dianhydride. .

The alkali-soluble resin may be used alone or in combination of two or more. It is preferable that the alkali-soluble resin has an acid value of 40 to 200 mgKOH/g and a weight average molecular weight of 1000 to 50,000 from the viewpoint of coating film formation and alkali developability.

The alkali-soluble resin may be suitably used in combination of one or two or more depending on the required performance.

Examples of the thermosetting resin or thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, phenol resin, Polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, cellulose, polybutadiene, polyimide resin, polyamideimide resin, benzoguanamine resin, melamine resin, urea Resin, etc. are mentioned.

As the photopolymerizable resin, a resin in which a photocrosslinkable group such as a (meth)acrylic compound or cinnamic acid is introduced into a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group through an isocyanate group, an aldehyde group, or an epoxy group is used. A polymer obtained by half-esterifying a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer with a (meth)acrylic compound having a hydroxyl group such as hydroxyalkyl (meth)acrylate Also used.

In the photopolymerizable compound, as a monomer having one photopolymerizable unsaturated bond in a molecule, for example, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, 2 -Alkyl methacrylates or acrylates such as ethylhexyl acrylate; Aralkyl methacrylate or acrylate such as benzyl methacrylate and benzyl acrylate; Alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate and butoxyethylacrylate; Aminoalkyl methacrylates or acrylates such as N,N-dimethylaminoethyl methacrylate and N,N-dimethylaminoethyl 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 ester or acrylic acid ester of polyalkylene glycol aryl ether such as hexaethylene glycol phenyl ether; Isobornyl methacrylate or acrylate; Glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate or acrylate, etc. are mentioned.

In the photopolymerizable compound, as a monomer having two or more photopolymerizable unsaturated bonds in the molecule, for example, bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimetha Crylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylol Propane trimethacrylate, 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 diacrylate, polyethylene glycol diacrylate, Polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate , Dipentaerythritol pentaacrylate, and the like.

(Carbon black)

The colored composition of the present invention may contain carbon black from the viewpoint of adjusting 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 manufactured by Orion Engineered Carbons, and MOGUL L manufactured by Cabot Corporation. , REGAL400R, TPK1101R, TPK1104R, TPK1227R, etc., and RAVEN1200, RAVEN1250, RAVEN1255, RAVEN1190U, RAVEN1170, RAVEN1035, RAVEN1080U, RAVEN1060U, RAVEN1100U, etc. manufactured by Columbian Carbon.

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, it is preferable that the particle diameter is 20 to 60 nm.

Examples of the acidic carbon black satisfying the above include NEROX2500, NEROX3500, TPK1101R, TPK1104R, TPK1227R, and the like.

In addition, the said particle diameter means the average primary particle diameter measured or calculated by microscopic observation.

Although the content of the acidic carbon black is not particularly limited, for example, it is preferably contained in an amount of 70% by mass or less based on the total mass of the pigments of the colored composition of the present invention. When the content of the acidic carbon black exceeds 70% by mass, the voltage retention may decrease or 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 total mass of the pigments in the coloring composition of the present invention.

Moreover, the coloring composition of this invention does not need to contain the said acidic carbon black.

The coloring composition of the present invention further comprises a pigment dispersant, a pigment dispersing aid represented by general formulas (1) and/or (2) described later, and/or a sulfonated product of copper phthalocyanine (which may be neutralized), and/or CI It is preferable to contain a pigment dispersion aid, a binder resin, and an organic solvent, which are the sulfonates of Pigment Yellow 138 (which may be neutralized).

(Pigment dispersant)

It is preferable that the coloring composition of this invention contains a pigment dispersant.

As the pigment dispersant, as a basic group-containing pigment dispersant, an anionic surfactant, a basic group-containing polyester pigment dispersant, a basic group-containing acrylic pigment dispersant, a basic group-containing urethane pigment dispersant, a basic group-containing carbodiimide pigment dispersant, acidic A group-containing polymeric pigment dispersant or the like can be used.

These basic group-containing pigment dispersants may be used alone or in combination of two or more. Among them, a basic group-containing polymeric pigment dispersant is preferred from the viewpoint of obtaining good pigment dispersibility.

As a specific example of the basic group-containing polymer pigment dispersant

(1) A polyester, polyamide having an amino group and/or an imino group and a free carboxyl group of a polyamine compound (for example, polyallylamine, polyvinylamine, poly(lower alkyleneamine) such as polyethylene polyimine), and At least one reaction product selected from the group consisting of polyesteramide (Japanese Patent Laid-Open No. 2001-59906),

(2) A reaction product of a low molecular weight amino compound such as poly(lower) alkyleneimine and methyliminobispropylamine, and a polyester having a free carboxyl group (Japanese Laid-Open Patent No. 54-37082, Japanese Laid-Open Patent No. 01- 311177 publication),

(3) Polyesters having one hydroxyl group such as alcohols such as methoxypolyethylene glycol or caprolactone polyester in the isocyanate group of the polyisocyanate compound, compounds having 2 to 3 isocyanate group reactive functional groups, isocyanate group reactive functional groups and agents A reaction product obtained by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound having a tertiary amino group (Japanese Laid-Open Patent Publication No. Hei 02-612),

(4) a compound obtained by reacting a polyisocyanate compound and a hydrocarbon compound having an amino group with a polymerized product 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 Laid-Open Patent Publication No. Hei 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 Laid-Open Patent Publication No. Hei 09-87537),

(8) a reaction product of a polycarbonate compound and a polyamine compound having a functional group capable of reacting with an amino group at one end (Japanese Laid-Open Patent Publication No. Hei 09-194585),

(9) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, At least one selected from methacrylic acid esters or acrylic acid esters such as stearyl acrylate and benzyl acrylate, acrylamide, methacrylamide, N-methylolamide, vinylimidazole, vinylpyridine, amino groups and polycapro A copolymer of at least one of a basic group-containing polymerization monomer such as a monomer having a lactone skeleton, and at least one of styrene, a styrene derivative, and other polymerizable monomers (Japanese Laid-Open Patent Publication No. 01-164429),

(10) basic group-containing carbodiimide pigment dispersant (International Publication No. WO04/000950),

(11) a block copolymer composed of a block having a basic group such as a tertiary amino group or a quaternary ammonium base and a block having no functional group (refer to the description of Japanese Patent Laid-Open No. 2005-55814),

(12) Pigment dispersant obtained by adding a polycarbonate compound to polyallylamine by Michael addition reaction (Japanese Laid-Open Patent Publication No. Hei 09-194585),

(13) a carbodiimide-based compound having at least one polybutadiene chain and at least one basic nitrogen-containing group (Japanese Laid-Open Patent No. 2006-257243),

(14) a carbodiimide compound having at least one side chain and a basic nitrogen-containing group each having an amide group in the molecule (Japanese Laid-Open Patent No. 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 by a quaternizing agent (Japanese Laid-Open Patent No. 2009-175613),

(16) A compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule and an active hydrogen group of a compound having an active hydrogen group in the molecule and a carbazole ring and/or an azobenzene skeleton, wherein the molecule of this compound A compound in which the number of carbazole rings and azobenzene skeletons is 15 to 85% of the sum of the urethane bonds and urea bonds generated by the reaction of an isocyanate group with an isocyanate group having an isocyanurate ring and an active hydrogen group ( Japanese patent application 2009-220836),

(17) Graft copolymers in which polyether or polyester side chains are introduced into an acrylate polymer having an amino group are mentioned.

Among the basic group-containing polymer pigment dispersants, a basic group-containing urethane-based polymer pigment dispersant, a basic group-containing polyester polymer pigment dispersant, and a basic group-containing acrylic polymer pigment dispersant are more preferred, and amino group-containing urethane-based polymer pigment dispersants, amino group-containing polyesters A polymer pigment dispersant and an amino group-containing acrylic polymer pigment dispersant are more preferable. Among the 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 a polyester chain, a polyether chain, and a polycarbonate chain is particularly preferable.

In the coloring composition of the present invention, the pigment dispersant is preferably 1 to 200 parts by mass, and more preferably 5 to 100 parts by mass, based on 100 parts by mass of the pigment.

(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 sulfonated product of copper phthalocyanine (which may be neutralized), and/or C.I. It is preferable to contain a pigment dispersion aid which is a sulfonated product of 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 is 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 may be substituted with other substituents, saturated or unsaturated having 1 to 10 carbon atoms. Represents an aliphatic hydrocarbon group 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.

When dispersing the pigment, excellent fluidity and stability over time can be obtained by using the pigment dispersing aid and the pigment dispersant together. Further, when the colored composition is used as a colored resist composition, it becomes possible to obtain a high optical density.

In the general formulas (1) and (2), 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 .

Regarding ``NR ¹ R ² R ³ R ⁴ '' (M) in the general formulas (1) and (2), R ¹ , R ² , R ³ and R ⁴ are the same or different and may be substituted with other substituents. It represents a 1-10 saturated or unsaturated aliphatic hydrocarbon group or a C6-C10 aromatic hydrocarbon group which may be substituted with another substituent. Here, as the saturated or unsaturated aliphatic hydrocarbon group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group Alkyl groups such as; Alkenyl groups such as vinyl group, allyl group, and 1-butenyl group; Alkynyl groups, such as ethynyl group and propynyl group, etc. are mentioned. As said aromatic hydrocarbon group, a phenyl group, a naphthyl group, etc. are mentioned. Moreover, as said other substituent, a hydroxyl group, a halogen, a carboxyl group, an amino group, a lower alkyl group (carbon number 1-5), etc. are mentioned.

In addition, ^{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.

In the above compound (pigment dispersion aid), the compound represented by the general formula (1) is an enol type, and the compound represented by the general formula (2) is a keto type tautomer, and the pigment dispersion aid includes two 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 formula (1) and (2).

Such pigment dispersion aids are novel compounds, 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, and heated to room temperature to 80 to 90°C, Next, the suspension obtained by dilution with a large amount of water can be filtered and washed with water to prepare a filter cake obtained by drying and pulverizing, and there is no commercial item.

Among these pigment dispersion aids, X in the above general formulas (1) and/or (2) is 2,5- from the viewpoint of obtaining a colored resist composition having a higher optical density as well as having good fluidity and stability over time. A compound represented by the following general formula (31) in which it is a dichlorophenyl group and Y is a phenyl group (a compound obtained by the above manufacturing method or the like using the monoazo compound of the above formula (3): enol type) and/or represented by the following general formula (32) A compound (a compound obtained by the above production method or the like using the monoazo compound of 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, and more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the pigment.

Even if the said pigment dispersion aid exceeds 30 mass parts with respect to 100 mass parts of said pigments, the pigment dispersion effect may not be improved.

(Organic solvent)

It is preferable that the coloring composition of this invention contains an organic solvent.

As the organic solvent, the solvent is an ester-based organic solvent having a boiling point of 70 to 300°C at normal pressure (1.013×10 ² kPa), an ether-based organic solvent, an ether ester-based organic solvent, a ketone-based organic solvent, and an aromatic hydrocarbon-based organic solvent. , Nitrogen-containing organic solvents and the like are preferable.

Specific examples of such solvents 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. , Propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, ether organic solvents such as diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol mono Ether ester-based organic solvents such as ethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl isobutyl ketone, cyclohexanone, 2-heptanone, δ-buty Ketone-based organic solvents such as lolactone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl ethylpropionate, 3-methyl-3-methoxybutylpropionate, 3- Ester-based organic solvents such as methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetate, n-amyl formic acid, N- Nitrogen-containing organic solvents such as methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide can be exemplified, and these organic solvents can be used alone or in combination of two or more. have.

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, in terms of boiling point, solubility, dispersibility, coating properties, etc. , Cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, 3-methoxy ethylpropionate, 3-ethoxy methylpropionate, n-amyl formate, etc. It is preferable, and propylene glycol monomethyl ether acetate is more preferable.

(Other additives)

Various additives, such as a photoinitiator, a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant, can be used suitably according to the manufacturing method of the coloring composition of this invention.

Although it does not specifically limit as said photoinitiator, For example, benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2, 2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chloro thioxanthone, 1-hydroxycyclohexyl Phenyl ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chlor-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2 -Benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, triazine photoinitiator, oxime ester photoinitiator, etc. can be used. These photoinitiators 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, more preferably 0.5 to 4% by mass, based on the total solid content.

<Production method of colored composition>

An example of a method for producing a colored composition using the above materials will be described.

As necessary, a binder resin, carbon black, a pigment dispersant, a pigment dispersant, an organic solvent, and other additives are added and mixed with each of the pigments of each color as necessary to obtain a mixture.

The obtained mixture is kneaded and dispersed using various dispersers such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high pressure disperser to obtain a pigment dispersion composition of each color.

Next, the obtained pigment dispersion composition of each color is mixed in a predetermined combination so that it becomes pseudo black, and if necessary, a binder resin, an organic solvent, and other additives are added and 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 production method, the binder resin can be added at the time of preparing the pigment dispersion composition. Moreover, it can also be added at the time of manufacture of a coloring composition after manufacture of a pigment dispersion composition.

(Covariance)

A mixture comprising a mixed pigment, a pigment dispersant, a pigment dispersion aid, an organic solvent, a binder resin as necessary, and other additives as necessary is obtained. The obtained mixture is kneaded and dispersed using various dispersers such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high pressure disperser to obtain a pigment dispersion composition.

Next, if necessary, a binder resin, an organic solvent, and other additives are added to the obtained pigment dispersion composition, uniformly mixed using a stirring device such as a high-speed stirrer, and filtered through a filter to obtain the colored composition of the present invention. In the above production method, the binder resin can be added at the time of preparing the pigment dispersion composition. Moreover, it can also be added at the time of manufacture of a coloring composition after manufacture of a pigment dispersion composition.

It is preferable that the viscosity of the coloring composition of this invention measured at 25 degreeC is 2.0-20.0mPa*s.

If the viscosity is less than 2.0 mPa·s or exceeds 20.0 mPa·s, the coatability may be adversely affected.

In addition, the viscosity is the viscosity measured using an E-type viscometer (manufactured by Toki Industries) after sealing the colored composition of the present invention with a lid on a glass bottle or the like and storing for 1 day.

It is preferable that the colored composition of the present invention has a aging stability of 0.8 to 1.1.

If the aging stability is less than 0.8 or exceeds 1.1, coating properties and developability may be adversely affected.

In addition, the aging stability is the viscosity at 25°C after sealing the colored composition of the present invention with a lid on a glass bottle or the like and storing at room temperature (25°C) for 1 day, and sealing the colored composition of the present invention with a lid on a glass bottle, etc. The viscosity at 25°C after storage at 40°C for 7 days is measured using an E-type viscometer (manufactured by Toki Industrial Co., Ltd.) as (Viscosity after storage at 40°C for 7 days)/(Viscosity after storage at room temperature for 1 day) I saved it.

Next, an example of using the colored composition of the present invention as a colored resist composition will be described.

The colored resist composition of the present invention contains 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 photoinitiator, and an organic solvent in addition to the colored composition of the present invention, and is preferably obtained by appropriately adding various additives such as a polymerization inhibitor if necessary.

<Constituent materials of the colored resist composition>

(Coloring composition)

The colored resist composition of the present invention is prepared by using the colored composition of the present invention.

The content of the colored composition of the present invention is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, based on the total solid content of the colored resist composition of the present invention.

(Pigment dispersant)

As the pigment dispersant, those described in the above 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 0.1 to 50 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total pigment 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 3 to 50 mass% in the solid content of the colored resist composition of the present invention.

(Photopolymerization initiator)

Although it does not specifically limit as a photoinitiator, For example, benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2 -Diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chloro thioxanthone, 1-hydroxycyclohexylphenyl Ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chlor-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2- Benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one), triazine-based photopolymerization initiator, Oxime ester photopolymerization initiator (ethanone, 　 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), etc.), etc. can be used. have. These photoinitiators can be used alone or in combination of two or more.

In the colored composition of the present invention, the photopolymerization initiator is preferably 0.1 to 10% by mass, 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 herein is preferably a compound having two or more ethylenically unsaturated bonds in a molecule from the viewpoint of polymerization and crosslinking properties. 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 suitably used.

In the colored resist composition of the present invention, the content of the organic solvent is preferably 5 to 90% by mass with respect to the total amount of the colored resist composition of the present invention from the viewpoints of solubility of each material, pigment dispersibility, coatability, and the like.

(Other additives)

Various additives, such as a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant, can be suitably used for the colored resist composition of this invention as needed.

<Method for producing the colored resist composition of the present invention>

The method for producing the 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 colored composition of the present invention and mixing by stirring using a stirring device or the like can be used.

It is preferable that the viscosity of the colored resist composition of the present invention measured at 25° C. is 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.

In addition, the viscosity is the viscosity measured using an E-type viscometer (manufactured by Toki Industries) after sealing the colored resist composition of the present invention with a lid on a glass bottle or the like and storing for 1 day.

The colored resist composition of the present invention preferably has a aging stability of 0.8 to 1.2.

If the aging stability is less than 0.8 or exceeds 1.2, coating properties and developability may be adversely affected. In addition, the aging stability is the viscosity at 25°C after sealing the colored resist composition of the present invention with a lid on a light-shielding glass bottle, etc., and storing at low temperature (5°C) for 1 day, and the coloring composition of the present invention, After sealing at low temperature (5℃) for 7 days, the viscosity at 25℃ was measured using an E-type viscometer (manufactured by Toki Industries) (viscosity after storage at 5℃ for 7 days)/(1 at 5℃). It was calculated as the viscosity after storage).

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 having a thickness of 1 μm is formed.

If the optical density (OD value) is 1.25 or higher, it can be said that the shielding property is sufficient.

In addition, the optical density (OD value) is a value measured by a Macbeth densitometer (TD-931, brand name, manufactured by Macbeth) by forming a 1 μm resist pattern using the colored resist composition of the present invention.

The colored resist composition of the present invention preferably has a solvent resistance of 0.6 or less, more preferably 0.5 or less, still more preferably 0.4 or less, particularly preferably 0.3 or less, and 0.2 or less when a cured coating film having a thickness of 2 μm is formed. Most preferred.

Further, the solvent resistance was immersed in N-methylpyrrolidone heated to 100° C. by a cured coating film having a thickness of 2 μm and kept warm for 10 minutes in an oven at 100° C. Thereafter, the absorbance of the N-methylpyrrolidone is measured with a spectrophotometer (UV-2500PC), and the absorbance of the maximum peak is taken as the value of solvent resistance.

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

Example

Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited thereto as long as it does not depart from the spirit and scope of application. In addition, unless otherwise noted, "parts" and "%" in this example represent "parts by mass" and "% by mass", respectively.

Materials of the coloring compositions used in Examples 1 to 10 and Comparative Examples 1 to 3 below are as follows.

<Pigment>

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 (made 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 mgKOH/g, mass average molecular weight: 10000)

<Pigment dispersant>

BYK-LPN-22102 (manufactured by Vicchemy, an acrylic block copolymer consisting of a segment having a pigment affinity group and a segment having a binder compatibility group)

<Pigment dispersion aid>

30 ml of concentrated sulfuric acid was put in a 100 ml Erlenmeyer flask, 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 stirred at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was added to a 1 L beaker, and the reaction was poured into the ice water, followed by stirring with a magnetic stirrer for 30 minutes. The resulting solid was dried by filtration and washing under reduced pressure to obtain 12 g of a pigment dispersion aid 1 (a compound represented by the general formula (31) and/or (32): M=H).

<Organic solvent>

PGMEA (Propylene Glycol Monomethyl Ether Acetate)

Materials of the colored resist compositions used in Examples 11 to 20 and Comparative Examples 4 to 6 below are as follows.

<Binder resin>

SPC-3500 (alkali-soluble resin, containing carbon=carbon unsaturated bond, 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, ethanol, 　1- 1 to 1 mixture of [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 the coloring composition of Examples 1-10 and Comparative Examples 1-3>

Various materials were mixed so that the composition of Table 1 (the amount of each material used in Table 1 was mass%), and softened day and night with a bead mill to prepare the coloring compositions of Examples 1 to 10 and Comparative Examples 1 to 3 Prepared.

<Preparation of colored resist compositions of Examples 11 to 20 and Comparative Examples 4 to 6>

Using a high-speed stirrer, the coloring compositions of Examples 1 to 10 and Comparative Examples 1 to 3 and other materials were uniformly mixed so that the composition of Table 2 (the amount of each material used in Table 2 is mass%), and then the hole Filtered through a filter having a diameter of 3 μm, to obtain colored resist compositions of Examples 11 to 20 and Comparative Examples 4 to 6.

(Evaluation test)

For 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, the fluidity and aging stability were evaluated by the following method, and the results are shown in Table 1 And shown in 2.

Further, the colored resist compositions obtained in Examples 11 to 20 and Comparative Examples 4 to 6 were coated to form a resist pattern, and the optical concentration and solvent resistance were evaluated, and the results are shown in Table 2.

<Liquidity>

Each of the colored compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 3 was collected in a glass bottle, sealed with a lid, and stored at room temperature (25°C) for 1 day, and then, using an E-type viscometer (manufactured by Toki Industries). The viscosity [mPa·s] at 25°C was measured to evaluate the fluidity.

Each of the colored resist compositions obtained in Examples 11 to 20 and Comparative Examples 4 to 6 was collected in a light-shielding glass bottle, sealed with a lid, and stored at low temperature (5°C) for 1 day, and then an E-type viscometer (manufactured by Toki Industries) was used. The viscosity [mPa·s] at 25°C was measured to evaluate the fluidity.

<Stability over time>

Each of the colored compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 3 was collected in a glass bottle, and the colored composition of the present invention was sealed with a lid on a glass bottle or the like, and then stored at room temperature (25° C.) for 1 day at 25°C. The viscosity at 25°C after sealing the colored composition of the present invention with a lid on a glass bottle or the like and storing at 40°C for 7 days was measured using an E-type viscometer (manufactured by Toki Industries) (7 at 40°C). It was calculated|required as the viscosity after 1 day storage)/(Viscosity after 1 day storage at room temperature).

In addition, for the colored resist compositions obtained in Examples 11 to 20 and Comparative Examples 4 to 6, the viscosity at 25°C after sealing with a lid on a light-shielding glass bottle or the like and storing at a low temperature (5°C) for 1 day, and the coloring of the present invention The composition was sealed with a lid on a light-shielding glass bottle, etc., and the viscosity at 25°C after storage at low temperature (5°C) for 7 days was measured using an E-type viscometer (manufactured by Toki Industries) (the 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 Comparative Examples 4 to 6 were coated on a glass substrate to a film thickness of 1 μm with a spin coater, prebaked at 100° C. for 3 minutes, and exposed with a high-pressure mercury lamp, furthermore at 230° C. Post-baking was performed for a minute to obtain a black resist pattern formed only with a beta portion. The optical density (OD value) of the black resist pattern of each of the obtained beta portions was measured with a Macbeth densitometer (TD-931, brand name, manufactured by Macbeth Corporation).

<solvent resistance>

The colored resist compositions of Examples 11 to 20 and Comparative Examples 4 to 6 were coated on a glass substrate to a film thickness of 1 μm with a spin coater, prebaked at 100° C. for 3 minutes, and exposed with a high-pressure mercury lamp, furthermore at 230° C. Post-baking was performed for a period of time to obtain a cured coating film formed only with a beta portion.

The obtained cured coating film of each beta part was immersed in N-methylpyrrolidone heated to 100°C, and kept warm in an oven at 100°C for 10 minutes. Thereafter, the absorbance of the N-methylpyrrolidone was measured with a spectrophotometer (UV-2500PC), and the absorbance of the maximum peak was taken as the value of solvent resistance.

It was confirmed that the colored composition and the colored resist composition according to the examples were excellent in flowability and stability over time.

Further, it was confirmed that the colored resist composition according to the example had an OD value of 1.25 or more and a solvent resistance of 0.60 or less, and was excellent in light-shielding property and solvent resistance.

Since the colored composition and the colored resist composition according to the examples have the above-described characteristics, they can be suitably used as black matrices such as image display devices and touch panels, black column spacers, or black partition wall materials.

On the other hand, in the colored composition and the colored resist composition according to the comparative example, there was no excellent light shielding property and excellent solvent resistance.

Advantageous Effects of Invention According to the present invention, it is possible to provide a colored composition having excellent light-shielding properties and excellent solvent resistance, and a colored resist composition containing the same.

Claims (4)

Including a pigment and a binder resin,
The pigment is at least one selected from the group consisting of CI pigment orange 16 and CI pigment yellow 139,
A colored composition comprising CI Pigment Blue 60. The method according to claim 1,
The pigment is a colored composition further comprising at least one selected from the group consisting of CI pigment violet 23 and CI pigment violet 29. A colored resist composition produced by using the colored composition according to claim 1 or 2. The colored composition according to claim 1 or 2, or the colored resist composition according to claim 3, which is used as a black matrix, a black column spacer, or a black partition material.