CN113939768A

CN113939768A - Coloring composition for black matrix and color filter

Info

Publication number: CN113939768A
Application number: CN202080042212.XA
Authority: CN
Inventors: 清水达彦; 井上智晶; 辻康人; 锅田智宏
Original assignee: Otsuka Chemical Co Ltd; Sakata Inx Corp
Current assignee: Otsuka Chemical Co Ltd; Sakata Inx Corp
Priority date: 2019-09-06
Filing date: 2020-08-20
Publication date: 2022-01-14
Also published as: WO2021044860A1; JP7308700B2; JP2021043250A; TW202116935A; KR20220060502A

Abstract

The technical problem is as follows: provided is a coloring composition for a black matrix, which has high dispersibility of a coloring material and generates little formaldehyde with time. The solution is as follows: a coloring composition for a black matrix, comprising a coloring material, a dispersant, a dispersion medium and a phosphite ester, wherein the phosphite ester is a compound represented by the general formula (5):

in the general formula (5), R⁵¹Represents a carbon atomAlkyl of 1 to 20 moles, R⁵²And R⁵³Each independently represents a hydrocarbon group, R⁵²And R⁵³Or may be bonded to each other to form a cyclic structure, and the compound represented by the general formula (5) may be represented by R⁵²Or R⁵³Bonding to form dimers or trimers.

Description

Coloring composition for black matrix and color filter

Technical Field

The present invention relates to a coloring composition for a black matrix.

Background

A color filter used in an image display device such as a liquid crystal display is composed of color pixels formed on a transparent substrate and transmitting light of three primary colors of red (R), green (G), and blue (B), and a black matrix formed at the boundary of each color pixel and substantially not transmitting visible light as black.

In the manufacture of a liquid crystal display, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a predetermined direction is formed thereon. In order to sufficiently obtain the properties of these transparent electrodes and alignment films, the formation of these transparent electrodes and alignment films needs to be performed at a high temperature of 200 ℃ or higher. Therefore, as a method for applying a coloring material to a transparent substrate of a color filter, a pigment dispersion method using a pigment having excellent heat resistance and light resistance as a coloring material is widely used.

In the above pigment dispersion method, a coloring composition in which a pigment, a dispersant, a binder resin, and a dispersion medium (solvent) are dispersed is used. When forming a colored layer, the colored composition is first coated on a transparent substrate, and a coating film formed of the colored composition is formed on the transparent substrate. Next, the binder resin is cured by irradiation with radiation (hereinafter referred to as "exposure") through a photomask having a desired pattern shape. Finally, the unexposed portion is removed by development to form a colored layer in a desired pattern shape. Further, the colored layer may be subjected to a treatment such as heating as necessary. In this way, by forming a pattern of black (hereinafter, referred to as a "black matrix") and color pixels of red (R), green (G), and blue (B), a color filter can be prepared.

The black matrix is formed in a lattice or a band shape, is a thin film or a fine part, and is required to have a sharp edge and high linearity. In recent years, a coloring composition using carbon black as a light-shielding material has been used for forming a black matrix. In order to maintain high light-shielding properties with a thin film, it is necessary to increase the content of carbon black. When carbon black is dispersed in a coloring composition, the carbon black tends to reaggregate with an increase in surface area, and the dispersion stability tends to decrease.

In order to solve this problem, a method of improving the affinity between the dispersion medium and carbon black in the coloring composition has been proposed, and various dispersants have been studied as a means for solving the problem. For example, the following compositions are proposed: a coloring composition using a polyurethane-based dispersant (see patent document 1), a coloring composition using a polyurethane-based dispersant having a basic functional group (see patent document 2), and a coloring composition using a dispersant composed of a polyester or polyether having a basic functional group (see patent document 3).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2000-227654

Patent document 2: japanese patent laid-open No. 2009-175613

Patent document 3: japanese patent laid-open publication No. 10-82908

Disclosure of Invention

Technical problem to be solved by the invention

In recent years, environmental standards have become more stringent, and a problem occurs in that formaldehyde is generated in the black matrix over time due to the colored composition. For example, in the conventional coloring compositions as disclosed in patent documents 1 to 3, the amount of formaldehyde in the coloring composition no longer satisfies the environmental standards.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a coloring composition for a black matrix, which has high dispersibility of a coloring material and generates less formaldehyde with time.

Means for solving the technical problem

The coloring composition for a black matrix according to the present invention, which can solve the above problems, is characterized by containing a coloring material, a dispersant, a dispersion medium, and a phosphite ester which is a compound represented by general formula (5).

In the general formula (5), R⁵¹Represents an alkyl group having 1 to 20 carbon atoms, R⁵²And R⁵³Each independently represents a hydrocarbon group, R⁵²And R⁵³Or may be bonded to each other to form a cyclic structure, and the compound represented by the general formula (5) may be represented by R⁵²Or R⁵³Bonding to form dimers or trimers.

By allowing the phosphite ester represented by the general formula (5) to coexist in the coloring composition, formaldehyde generated from the compounding agent and the phosphite ester react irreversibly, thereby reducing formaldehyde in the coloring composition.

Effects of the invention

According to the present invention, a coloring composition for a black matrix, which has high dispersibility of a coloring material and generates less formaldehyde with time, can be obtained.

Detailed Description

Next, an example of a preferred embodiment of the present invention will be described. The following embodiments are merely examples. The present invention is not limited to the following embodiments. In the present invention, "(meth) acrylic acid" means "at least one of acrylic acid and methacrylic acid". "(meth) acrylate" means "at least one of acrylate and methacrylate".

< coloring composition for black matrix >

The coloring composition for a black matrix (hereinafter, may be simply referred to as "coloring composition") of the present invention is characterized by containing a coloring material, a dispersant, a dispersion medium, and a phosphite ester which is a compound represented by general formula (5).

Conventional coloring compositions generate formaldehyde over time due to compounding agents in the coloring compositions. Here, by making the general formula (5) representation of the phosphite ester coexisting, from the compounding agent generated from formaldehyde and phosphite ester irreversible reaction. Therefore, formaldehyde in the coloring composition can be reduced.

Preferably, the coloring composition for a black matrix is substantially opaque to visible light. Specifically, the optical density (OD value) of the black resist pattern formed from the coloring composition is preferably 0.5 or more, more preferably 1.0 or more, and still more preferably 1.5 or more. The optical density was measured by applying the coloring composition onto a glass substrate with a film thickness of 1 μm by a spin coater, forming a black resist pattern only on the solid portion, and measuring the black resist pattern with a Macbeth densitometer (TD-931, manufactured by Macbeth corporation).

Next, various components and the like of the coloring composition for a black matrix of the present invention will be described.

[ coloring Material ]

The coloring material is not particularly limited as long as it can change the coloring composition into black or into a hue simulating black, and a known coloring material can be used. Here, the "pseudo-black hue" means ideally black, but may be any hue that is acceptable for a black matrix that is a color filter used in a liquid crystal display element. As a black matrix, it is necessary to be substantially achromatic, with no extra color added. Further, since the contrast of an image is lowered when light leakage occurs from the black matrix, the black matrix is preferably black in view of absorbing all the respective color lights as described above. However, if the color is not completely achromatic, the color may be in a hue range in which no extra color is added to the image. Further, a hue capable of absorbing necessary light so as to maintain contrast is included in a hue range simulated as black.

Examples of the coloring material include a black pigment, a mixed color pigment, and a mixture thereof.

Examples of the black pigment include carbon black, graphite, perylene pigments, lactam pigments, titanium black, and metal oxides, composite oxides, metal sulfides, metal sulfates, and metal carbonates of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver. Among them, carbon black and titanium black are preferable from the viewpoint of light-shielding rate and image characteristics. Examples of the carbon black include furnace black, channel black, acetylene black, thermal black, lamp black, and bone black. The carbon black may be either neutral carbon black or acidic carbon black, or both of them may be used. The hue of the black pigment is not limited to black having an achromatic color in terms of colorimetry, and may be purplish black, bluish black, or reddish black.

As the mixed color pigment, there can be mentioned a pigment in which two or more pigments other than the black pigment are mixed to simulate black. The mixed color pigment may be a pigment in which two or more organic pigments selected from a blue organic pigment, a violet organic pigment, a yellow organic pigment, a red organic pigment and an orange organic pigment are mixed to simulate black.

Examples of the Blue organic pigment include c.i. pigment Blue (c.i. pigment Blue)1, 1: 2. 9, 14, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 17, 19, 22, 25, 27, 28, 29, 33, 35, 36, 56: 1. 60, 61: 1. 62, 63, 64, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc.

Examples of the Violet organic pigment include c.i. pigment Violet (c.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, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49, 50, etc.

Examples of the Yellow organic pigment include c.i. pigment Yellow (c.i. pigment Yellow)1, 1: 1. 2, 3,4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35: 1. 36, 36: 1. 37, 37: 1. 40, 41, 42, 43, 48, 53, 55, 61, 62: 1. 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127: 1. 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191: 1. 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 213, etc.

Examples of the Red organic pigment include c.i. pigment Red (c.i. pigment Red)1, 2, 3,4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48: 1. 48: 2. 48: 3. 48: 4. 49, 49: 1. 49: 2. 50: 1. 52: 1. 52: 2. 53, 53: 1. 53: 2. 53: 3. 57 and 57: 1. 57: 2. 58: 4. 60, 63: 1. 63: 2. 64, 64: 1. 68, 69, 81: 1. 81: 2. 81: 3. 81: 4. 83, 88, 90: 1. 97, 101: 1. 104, 108: 1. 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 184, 185, 187, 188, 190, 192, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 230, 231, 232, 233, 235, 236, 237, 238, 239, 240, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 270, 271, 272, 273, 274, 275, 269, and the like.

Examples of Orange organic pigments include c.i. pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 51, 55, 59, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like.

As the combination of the organic pigments, a combination of a blue organic pigment and at least two or more organic pigments selected from the group consisting of violet, yellow, red and orange organic pigments is preferable.

The coloring material may also contain a pigment derivative as a dispersion aid. The pigment derivative preferably contains a pigment derivative having an acidic group. The dye derivative is a substance having an acidic functional group introduced into a dye skeleton. Specific examples of the pigment skeleton include azo-based pigment skeleton, phthalocyanine-based pigment skeleton, anthraquinone-based pigment skeleton, triazine-based pigment skeleton, acridine-based pigment skeleton, perylene-based pigment skeleton, and the like. The acidic group introduced into the dye skeleton is preferably a carboxyl group, a phosphate group, or a sulfonate group. In view of ease of synthesis and the strength of acidity, a sulfonic acid group is preferable. The acidic group may be bonded directly to the pigment skeleton, but may be bonded to the pigment skeleton via a hydrocarbon group such as an alkyl group or an aryl group, an ester group, an ether group, a sulfonamide group, or a urethane bond.

The total content of the coloring material in the coloring composition is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, of the total solid content of the coloring composition. The solid component herein means a component other than the dispersion medium described later in the coloring composition.

[ dispersing agent ]

The coloring composition contains a dispersant. The dispersant has the following two sites: one site has a property of adsorbing to the coloring material, and the other site has an affinity with the dispersion medium. The dispersant adsorbs to the coloring material and has a function of stabilizing dispersion in the dispersion medium. The dispersing agent is not particularly limited and may be appropriately selected depending on the kinds of the coloring material and the dispersion medium. As the dispersant, a resin type dispersant used in the color composition for a color filter can be used, and examples thereof include a polyester resin type dispersant, (meth) acrylic resin type dispersant, a polyurethane resin type dispersant, a polyallylamine resin type dispersant, and a carbodiimide resin type dispersant.

Examples of the resin type dispersant include the following dispersants.

(1) A reaction product of an amino group and/or an imino group of a polyamine compound (e.g., a polyalkyleneamine such as polyallylamine, polyvinylamine, and polyethylenepolyimine) and at least one selected from a polyester, a polyamide, and a polyesteramide having a free carboxyl group.

(2) A carbodiimide compound having at least one side chain selected from the group consisting of a polyester side chain, a polyether side chain and a polyacrylic side chain and a basic nitrogen-containing group in each molecule.

(3) The reaction product of an amine compound such as polyalkyleneimine or methyliminodipropylamine and a polyester having a free carboxyl group.

(4) A reaction product obtained by reacting a polyester having 1 hydroxyl group such as an alcohol such as methoxypolyethylene glycol or a caprolactone polyester, a compound having 2 to 3 isocyanate group-reactive functional groups, and an aliphatic or heterocyclic hydrocarbon compound having an isocyanate group-reactive functional group and a tertiary amino group with an isocyanate group of a polyisocyanate compound in this order.

(5) A reaction product obtained by reacting a polyisocyanate compound and a hydrocarbon compound having an amino group with a polymer of an acrylate having an alcoholic hydroxyl group.

(6) A reaction product obtained by adding a polyether chain to an amine compound.

(7) A reaction product obtained by reacting a compound having an amino group with a compound having an isocyanate group.

(8) A reaction product obtained by reacting a linear polymer having free carboxyl groups and an organic amine compound having 1 secondary amine group with a polyepoxide.

(9) A reaction product of a polycarbonate compound having a functional group reactive with an amino group at one terminal side and a polyamine compound.

(10) A copolymer of at least one kind selected from (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octadecyl (meth) acrylate, benzyl (meth) acrylate, and the like, and at least one kind selected from polymerizable monomers having a basic group such as (meth) acrylamide, N-methylolamide, vinylimidazole, vinylpyridine, monomers having an amino group and a polycaprolactone skeleton, and at least one kind selected from styrene, a styrene derivative, and other polymerizable monomers.

(11) A (meth) acrylic block copolymer comprising a block having a basic group such as a tertiary amino group or a quaternary ammonium group and a block having no basic functional group.

(12) A compound obtained by Michael addition of a polycarbonate compound to polyallylamine.

(13) A carbodiimide-based compound having at least one polybutadiene chain and a basic nitrogen-containing group, respectively.

(14) A carbodiimide compound having at least one side chain having an amide group and a basic nitrogen-containing group in each molecule.

(15) A polyurethane-based compound having a structural unit containing an ethylene oxide chain and a propylene oxide chain and having an amino group quaternized by a quaternizing agent.

(16) And a compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in a molecule with an active hydrogen group of a compound having an active hydrogen group and a carbazole ring and/or an azobenzene skeleton in a molecule, wherein the number of the carbazole ring and the azobenzene skeleton is 15 to 85% based on the total of the isocyanate group of the isocyanate compound having an isocyanurate ring in the molecule and an urethane bond and a urea bond generated by the reaction of the isocyanate group with the active hydrogen group.

Among these resin type dispersants, polyurethane type resin type dispersants containing a basic group, polyester type resin type dispersants containing a basic group, and (meth) acrylic resin type dispersants containing a basic group are more preferable, and polyurethane type resin type dispersants containing an amino group, polyester type resin type dispersants containing an amino group, and (meth) acrylic resin type dispersants containing an amino group are further preferable. Particularly preferred is a polyurethane resin type dispersant containing a basic group, and preferred is a polyurethane resin type dispersant containing a basic group (amine group) selected from at least one of a polyester chain, a polyether chain and a polycarbonate chain.

The resin type dispersant is preferably a resin (polymer) having a polar functional group. It is considered that the polar functional group adsorbs to the pigment and has an effect of stabilizing dispersion in the dispersion medium. Examples of the polar functional group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium salt group, an imino group, an amide group, a nitrogen-containing heterocyclic group, a carboxyl group, a phosphoric acid group, and a sulfonic acid group. The polar functional group is preferably at least one selected from the group consisting of a primary amine group, a secondary amine group, a tertiary amine group, a quaternary ammonium salt group, an imine group, an amide group, and a nitrogen-containing heterocyclic group.

As the resin type dispersant, there are the following polymers: a polymer having an amine value but not having an acid value (a polymer having an amine value of more than 0mgKOH/g and an acid value of 0mgKOH/g), a polymer having an acid value but not having an amine value (a polymer having an acid value of more than 0mgKOH/g and an amine value of 0mgKOH/g), a polymer having an amine value and an acid value (a polymer having an amine value and an acid value of more than 0mgKOH/g), and a polymer having an acid value and an amine value (a polymer having an amine value and an acid value of 0 mgKOH/g).

As the above-mentioned resin type dispersant, a polymer having an amine value (a polymer having an amine value of more than 0mgKOH/g) is preferable. The amine value of the resin type dispersant is preferably 10mgKOH/g or more and 200mgKOH/g or less. When the amine value is not less than 10mgKOH/g, the dispersion stabilizing effect is further improved, and when the amine value is not more than 200mgKOH/g, the solubility of the coloring composition in an alkali-developable solution is good, and the pattern processability is improved. Further, the acid value of the resin type dispersant is preferably less than 20 mgKOH/g.

The content of the dispersant in the coloring composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 5 parts by mass or more, particularly preferably 10 parts by mass or more, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, relative to 100 parts by mass of the coloring material.

[ dispersing Medium ]

The coloring composition contains a dispersion medium. The dispersion medium may be appropriately selected and used as long as it can disperse or dissolve other components (solid components) constituting the coloring composition, does not react with these components, and has appropriate volatility. As the dispersion medium, for example, conventionally known organic solvents can be used, and examples thereof include: glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, 1-methoxy-2-propanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol monomethyl ether; glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol mono-n-butyl ether acetate, methoxybutyl acetate, methoxyamyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; glycol diacetate esters such as ethylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate; alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether; ketones such as acetone, methyl ethyl ketone, 2-heptanone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentanone; monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerol, benzyl alcohol, and diacetone alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; chain or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methyl-3-methoxypropionate, γ -butyrolactone, and ethyl 2-hydroxypropionate; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as chlorinated butane and chlorinated pentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile.

The organic solvent is preferably diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, amyl formate, ethyl 2-hydroxypropionate, butyl 3-methyl-3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, or the like, from the viewpoints of dispersibility of a coloring material or the like, solubility of a dispersant, coatability of a coloring composition, and the like. The dispersion medium contained in the coloring composition may be only one kind or may be plural kinds.

The content of the dispersion medium in the coloring composition is not particularly limited and may be appropriately adjusted. The content of the dispersion medium in the coloring composition is usually 99% by mass or less. In addition, the content of the dispersion medium in the coloring composition is preferably 50% by mass or more in view of the viscosity suitable for coating the coloring composition.

[ phosphite ]

The coloring composition of the present invention contains a phosphite ester represented by the general formula (5). By containing a phosphite, formaldehyde generated from a compounding agent in the coloring composition can be reduced.

R⁵¹Represents an alkyl group having 1 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, an isoundecyl group, a dodecyl group, an isododecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, an isotetradecyl group, a hexadecyl group, an isohexadecyl group, an octadecyl group, an isostearyl group, and an eicosyl group. Among them, ethyl, butyl and isodecyl groups are preferable.

As R⁵²Or R⁵³Examples of the hydrocarbon group include an alkyl group which may have a substituent and an aromatic group which may have a substituent. The total number of carbon atoms of the alkyl group which may have a substituent is preferably 1 to 20, more preferably 1 to 15. Examples of the alkyl group include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, an isoundecyl group, a dodecyl group, an isododecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, an isotetradecyl group, a hexadecyl group, an isohexadecyl group, an octadecyl group, an isostearyl group, and an eicosyl group; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl and methylcyclohexyl. As the fragranceExamples of the group include a phenyl group, a tolyl group, a xylyl group, a cumyl group, a mesityl group, a benzyl group, a phenethyl group, a styryl group, a cinnamyl group, a benzhydryl group, a trityl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl group, an undecylphenyl group, and a dodecylphenyl group.

R⁵²And R⁵³Or bonded to each other to form a ring structure. As R⁵²And R⁵³The rings formed by bonding to each other include, for example, the following partial structures. Further, the compound represented by the general formula (5) may be represented by R⁵²Or R⁵³Bonding to form dimers or trimers.

The phosphite ester represented by the above general formula (5) is preferably a phosphite ester represented by the general formula (5-1) and/or a phosphite ester represented by the general formula (5-2).

In the general formula (5-1), R⁵¹Represents an alkyl group having 1 to 20 carbon atoms, a plurality of R' s⁵¹May be the same or different.

In the general formula (5-2), R⁵¹Represents an alkyl group having 1 to 20 carbon atoms, a plurality of R' s⁵¹May be the same or different.

Examples of the phosphite ester represented by the above general formula (5) include trialkyl phosphites such as triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, trioctyl phosphite, triisooctyl phosphite, trinonyl phosphite, tridecyl phosphite, and triisodecyl phosphite; alkyl diphenyl phosphites such as octyl diphenyl phosphite, decyl diphenyl phosphite, diphenylisodecyl phosphite, tridecyl diphenyl phosphite, and hexadecyl diphenyl phosphite; and dimers of phosphites such as 3, 9-bis (octadecyloxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5,5] undecane, and 3, 9-bis (isodecyloxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5,5] undecane. Among them, trialkyl phosphite is preferable, and triethyl phosphite, tributyl phosphite, and triisodecyl phosphite are more preferable.

The phosphite ester represented by the general formula (5) contained in the coloring composition may be only one kind or may be plural kinds.

The content of the phosphite ester represented by the general formula (5) in the coloring composition is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 1 part by mass or more, particularly preferably 5 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, further preferably 60 parts by mass or less, and particularly preferably 25 parts by mass or less with respect to 100 parts by mass of the dispersant.

When the coloring composition is formulated, the phosphite may be added to the coloring material and/or the dispersant before the coloring material and the dispersant are mixed, may be added while the coloring material and the dispersant are mixed, or may be added to the mixture after the coloring material and the dispersant are mixed.

[ phenol-based antioxidant ]

The coloring composition of the present invention may contain a known phenol antioxidant. The amount of formaldehyde in the coloring composition can be further reduced by containing a phenol-based antioxidant. It is considered that the reason why the amount of formaldehyde can be reduced is because oxidative deterioration of phosphite can be suppressed. Further, by containing the phenolic antioxidant, even when the coloring composition contains a binder resin in a large amount, the dispersion stability of the coloring material can be improved. In particular, when the binder resin content in the total solid content of the coloring composition is 30% by mass or more, the effect of improving the dispersion stability is more remarkable.

The phenolic antioxidant refers to an antioxidant having a compound having at least one hydroxyl group on at least one benzene ring. Specific examples thereof include antioxidants having the following chemical structures: when the hydroxyl group on the benzene ring is the 1-position, at least one of the 2-, 4-and 6-positions or at least one of the 3-, 4-and 6-positions has a substituent capable of blocking other molecules having a radical, for example, a bulky substituent (for example, a substituent in which the carbon atom bonded to the benzene ring is a quaternary carbon atom (specifically, t-butyl group, adamantyl group, etc.)).

As the phenol-based antioxidant, a compound represented by the general formula (6) is preferable.

In the general formula (6), R⁶¹Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, wherein R⁶¹The carbon atom bonded with the benzene ring of (1) is a primary to tertiary carbon atom, R⁶²R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms⁶³The hydrocarbon group is a group in which at least one carbon atom of a hydrocarbon group having 2 to 20 carbon atoms is substituted with an ester group or an ether group, or a hydrocarbon group having 1 to 20 carbon atoms, and n represents a number of 1 to 6.

R⁶¹Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, and an isooctyl group. Among these, from the viewpoint of a large synergistic effect of the oxygen-resisting property, a hydrogen atom, a methyl group, and an ethyl group are preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is further preferable. To be described, R⁶¹The carbon atom bonded to the benzene ring is not a quaternary carbon atom, and a group such as t-butyl is not suitable as R⁶¹。

R⁶²Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tert-butyl group, and a methyl group is preferable.

R⁶³The hydrocarbon group is a group in which at least one carbon atom of a hydrocarbon group having 2 to 20 carbon atoms is substituted with an ester group or an ether group, or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, isoundecyl, dodecyl, isododecyl, tridecyl, isotridecyl, tetradecyl, isotetradecyl, hexadecyl, isohexadecyl, octadecyl, isooctadecyl, and eicosyl; alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl and the like; aryl groups such as phenyl, tolyl, xylyl, cumyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl and the like; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl and methylcyclohexyl. Among them, an alkyl group is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. The group is a group represented by the general formula (6) wherein n has a value of 1, a group wherein any one hydrogen atom is removed from the group when n has a value of 2, and a group wherein any two hydrogen atoms are removed from the group when n has a value of 3. The value of n is a number of 1 to 6, but from the viewpoint of satisfactory performance as an antioxidant and satisfactory raw material, a number of 1 to 4 is preferred, and a number of 2 or 3 is more preferred.

R⁶³The hydrocarbon group may have at least one carbon atom of a hydrocarbon group having 2 to 20 carbon atoms substituted with an ester group or an ether group. The group may have only one of an ester group and an ether group, both of them, or a plurality of them. In view of the synergistic effect with phosphite, R is described⁶³The hydrocarbon group preferably has 1 to 20 carbon atoms.

Specific examples of the compound of the general formula (6) include 1,1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 4' -butylidenebis (6-t-butyl-m-cresol), [ ethylenebis (oxyethylene) ] bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate ], bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid ] (2,4,8, 10-tetraoxaspiro [5,5] undecane-3, 9-diyl) bis (2, 2-dimethyl-2, 1-ethanediyl)) ester, and the like.

The phenolic antioxidant contained in the coloring composition may be one kind or plural kinds.

The content of the phenolic antioxidant in the coloring composition is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 1 part by mass or more, preferably 25 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 2 parts by mass or less, with respect to 100 parts by mass of the dispersant.

When the coloring composition is prepared, the phenolic antioxidant may be added to the coloring material and/or the dispersant before the coloring material and the dispersant are mixed, may be added while the coloring material and the dispersant are mixed, or may be added to the mixture after the coloring material and the dispersant are mixed. The phenolic antioxidant is preferably added to the coloring material and/or the dispersant before the coloring material and the dispersant are mixed.

[ Binder resin ]

The coloring composition of the present invention may contain a binder resin (excluding the above-mentioned dispersant). Examples of the binder resin include alkali-soluble resins, polymerizable compounds (polymerizable resins, monomers having one polymerizable unsaturated bond in the molecule, monomers having two or more polymerizable unsaturated bonds in the molecule, oligomers, and the like), thermosetting resins, thermoplastic resins, and the like. These may be used alone or in combination of two or more. Among them, alkali-soluble resins and/or polymerizable compounds are preferable.

The binder resin is a compound different from the above resin-type dispersant. The binder resin is preferably a binder resin having an amine value of 0 mgKOH/g.

The content of the binder resin in the coloring composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less, based on the total amount of the binder resin used, in the total solid content of the coloring composition.

(alkali-soluble resin)

The alkali-soluble resin is not particularly limited as long as it functions as a binder for the coloring material and is soluble in a developer used in a development process of the color filter, preferably an alkali developer, when the color filter is produced. The alkali-soluble resin is preferably a resin having an acidic group such as a carboxyl group or a phenolic hydroxyl group.

Examples of the alkali-soluble resin include: a resin obtained by adding an unsaturated monobasic acid to at least a part of epoxy groups of a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, or a resin obtained by adding a polybasic acid anhydride to at least a part of hydroxyl groups generated by the addition reaction; a linear resin having a carboxyl group in the main chain; a resin obtained by adding an epoxy group-containing unsaturated compound to a carboxyl group of a carboxyl group-containing resin; (meth) acrylic resins; epoxy (meth) acrylate resins having a carboxyl group, and the like. These may be used alone or in combination of two or more.

Specific examples of the alkali-soluble resin include: and acid group-containing copolymer resins obtained by radical polymerizing an acid group-containing unsaturated monomer component with at least one monomer component selected from the group consisting of styrene, methylstyrene, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, methyl (meth) acrylate, polystyrene macromonomer, and polymethyl (meth) acrylate macromonomer. Examples of the acid group-containing unsaturated monomer component include (meth) acrylic acid, itaconic acid, maleic anhydride, monoalkyl maleate, citraconic acid, citraconic anhydride, monoalkyl citraconate, sulfoethyl (meth) acrylate, butyl (meth) acrylamide sulfonic acid, sulfoethyl (meth) acrylate, and the like.

The alkali-soluble resin may be a resin having a carbon-carbon double bond in a side chain, which can undergo radical polymerization. By having a double bond in a side chain, the photocurable property of the colored composition of the present invention is improved, and therefore, the resolution and the adhesion can be further improved. Examples of the method for introducing a carbon-carbon double bond capable of radical polymerization into the side chain include a method in which a compound such as glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, or o- (or m-or p-) vinylbenzyl glycidyl ether is reacted with an acidic group of the alkali-soluble resin.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 500 or more, more preferably 1,000 or more, preferably 200,000 or less, and more preferably 100,000 or less. When the Mw of the alkali-soluble resin is 500 or more, the heat resistance, film strength and the like of a colored layer formed from the colored composition are good, and when the Mw is 200,000 or less, the alkali developability of the coating film is better.

The acid value of the alkali-soluble resin is preferably not less than 10mgKOH/g, more preferably not less than 20mgKOH/g, preferably not more than 300mgKOH/g, and more preferably not more than 200 mgKOH/g. When the acid value of the alkali-soluble resin is not less than 10mgKOH/g, the alkali developability is more excellent when the colored composition is used as a colored layer, and when it is not more than 300mgKOH/g, the film strength and the like are excellent. Further, the amine value of the alkali-soluble resin is preferably less than 10 mgKOH/g.

The content of the alkali-soluble resin in the coloring composition is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, further preferably 30 parts by mass or more, preferably 200 parts by mass or less, and more preferably 120 parts by mass or less, relative to 100 parts by mass of the coloring material. The content of the alkali-soluble resin in the coloring composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, of the total solid content of the coloring composition.

(polymerizable Compound)

As the polymerizable resin of the polymerizable compound, there can be used: a resin obtained by introducing a crosslinkable group such as a (meth) acrylic compound or cinnamic acid into a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group via an isocyanate group, an aldehyde group or an epoxy group. It is also possible to use: 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 a hydroxyalkyl (meth) acrylate.

Examples of the monomer having one polymerizable unsaturated bond in the molecule of the polymerizable compound include alkyl (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as butoxyethyl (meth) acrylate; aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate; (meth) acrylic acid esters of polyalkylene glycol alkyl ethers such as diethylene glycol ethyl ether, triethylene glycol butyl ether, and dipropylene glycol methyl ether; (meth) acrylic acid esters of polyalkylene glycol aryl ethers such as hexaethylene glycol phenyl ether; isobornyl (meth) acrylate; glycerol (meth) acrylate; 2-hydroxyethyl (meth) acrylate, and the like.

The polymerizable compound is a monomer having two or more polymerizable unsaturated bonds in the molecule, examples thereof include bisphenol a di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like.

The content of the polymerizable compound in the coloring composition is preferably 3% by mass or more, more preferably 5% by mass or more, preferably 50% by mass or less, and more preferably 20% by mass or less, in the total solid content of the coloring composition. If the content of the polymerizable compound is too small, sufficient curability may not be obtained. On the other hand, if the amount of the polymerizable compound is too large, the alkali developability of the coloring composition of the present invention is lowered, and the base stain, film residue, and the like tend to occur easily on the substrate or the light-shielding layer in the unexposed portion.

(thermosetting resin, thermoplastic resin)

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

[ photopolymerization initiator ]

The coloring composition preferably contains a photopolymerization initiator. Thereby imparting radiation sensitivity to the color composition. The photopolymerization initiator is a compound which generates an active substance capable of initiating polymerization of the crosslinking agent by exposure to radiation such as visible light, ultraviolet rays, far infrared rays, electron rays, X-rays, and the like.

Examples of the photopolymerization initiator include thioxanthone compounds, acetophenone compounds, bisimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -diketone compounds, polyquinone compounds, diazo compounds, imide sulfonate compounds, and amino ketone compounds. The photopolymerization initiators may be used singly or in combination of two or more.

The content of the photopolymerization initiator in the coloring composition of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 20% by mass or less, and more preferably 10% by mass or less, in the total solid content of the coloring composition. In this case, if the content of the photopolymerization initiator is too small, the exposure curing may be insufficient, and if the content is too large, the formed colored layer may be easily detached from the substrate during development.

[ other compounding Agents ]

Examples of the other compounding agents include sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, plasticizers, organic carboxylic acid compounds, organic carboxylic acid anhydrides, pH adjusters, antioxidants other than the above phenolic antioxidants, ultraviolet absorbers, light stabilizers, preservatives, mold inhibitors, anti-aggregation agents, adhesion modifiers, development modifiers, and storage stabilizers.

[ method for producing coloring composition ]

The coloring composition can be prepared by mixing a coloring material, a dispersant, a dispersion medium, a phosphite, and, if necessary, a phenolic antioxidant, a binder resin, a photopolymerization initiator, a light diffusing agent (e.g., precipitated barium sulfate), and other compounding agents. For example, a paint mixer, a bead mill, a ball mill, a dissolver, a kneader, or the like can be used for mixing. The colouring composition is preferably filtered after mixing. The method of mixing the materials is not particularly limited, and examples thereof include the following methods: a method of mixing all materials together at the same time; a method of mixing a coloring material, a dispersant and a dispersion medium to disperse the coloring material in advance, and then mixing another material in the coloring material dispersion liquid; a method of preparing a coloring material dispersion base liquid by mixing a coloring material, a dispersant and a part of other materials, and then mixing the other materials with the coloring material dispersion base liquid. The coloring composition has excellent dispersibility and can be suitably used for a black matrix because the generation of formaldehyde is suppressed.

< color Filter >

The color filter of the present invention includes, on a transparent substrate, color pixels that transmit light of three primary colors of red (R), green (G), and blue (B), and a black matrix formed of the colored composition.

As a method for producing a color filter, for example, the following method can be cited. First, the color composition for a black matrix of the present invention is applied to a transparent substrate such as a thermoplastic resin sheet such as a polyester resin, a polyolefin resin, a polycarbonate resin, or a polymethyl methacrylate resin, a thermosetting resin sheet such as an epoxy resin, an unsaturated polyester resin, or a poly (meth) acrylic resin, or various glasses, and then soft baked (pre-bake) to evaporate a solvent (dispersion medium) to form a coating film. Next, the coating film is exposed through a photomask, and then developed with an alkali developing solution (an aqueous solution containing an organic solvent, a surfactant, and an alkali compound) to dissolve and remove the unexposed portion of the coating film, thereby forming a black pattern (black matrix). Then, after hard-baking (post-bake) as necessary, the same operation is sequentially repeated for red (R), green (G), and blue (B), thereby obtaining a color filter in which a pixel array of three primary colors of red, green, and blue is arranged on a substrate. However, the order of forming each color pixel in the present invention is not limited to the above order.

When the coloring composition is applied to the substrate, an appropriate coating method such as a spray coating method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or the like can be used, but the spin coating method and the slit die coating method are particularly preferably used.

After a protective film is formed as necessary on the pixel pattern obtained in this way, a transparent conductive film (ITO (indium tin oxide) or the like) is formed by sputtering. After the transparent conductive film is formed, a partition plate can be further formed to manufacture a color filter.

The color filter of the present invention can be suitably used for a color liquid crystal display element, a color camera tube element, a color sensor, an organic electroluminescence display element, electronic paper, and the like, because the generation of formaldehyde is suppressed and the dimensional accuracy is high.

Examples

The present invention will be described in further detail with reference to specific examples. The present invention is not limited to the following examples, and can be carried out with appropriate modifications within a range not changing the gist thereof.

< evaluation method >

(Dispersion stability)

The pigment dispersion base liquid and the coloring composition were collected in glass bottles, tightly closed, and stored at room temperature for 7 days. The pigment dispersion base liquid and the coloring composition after storage were visually observed and evaluated according to the following evaluation criteria.

A: no thickening and settling was found.

B: tackified or settled material that is recoverable if gently shaken was found.

C: thickening or settling was found which could not be recovered even by severe vibration.

(developability of resist Pattern)

Each of the colored compositions was applied to a glass substrate at a film thickness of 1 μm by a spin coater, and the resultant was softened at 100 ℃ for 3 minutes. Then, using a ratio of the area of the obtained cured portion to the uncured portion of 20: 80 line width of the mask having a lattice pattern of 25 μm was subjected to UV light accumulation of 400mJ/cm using a high-pressure mercury lamp²And (6) carrying out exposure. The resultant coating was developed using a 0.05% aqueous potassium hydroxide solution, and the developability was evaluated according to the following evaluation criteria, depending on the time for which the unexposed portion of the coloring composition was removed.

A: can be completely removed within 30 seconds.

B: complete removal can be achieved in more than 30 seconds and 60 seconds.

C: it cannot be completely removed even for more than 60 seconds.

(development latitude of resist Pattern)

Each of the colored compositions was applied to a glass substrate at a film thickness of 1 μm by a spin coater, and the resultant was softened at 100 ℃ for 3 minutes. Then, using a ratio of the area of the obtained cured portion to the uncured portion of 20: 80 line width of the mask having a lattice pattern of 25 μm was subjected to UV light accumulation of 400mJ/cm using a high-pressure mercury lamp²And (6) carrying out exposure. The resultant coating was developed using a 0.05% aqueous potassium hydroxide solution, and the time from when the unexposed portion of the coloring composition was removed until the removal of the resist composition of the cured portion occurred was measured, and the development latitude was evaluated according to the following evaluation criteria.

A: the time from when the coloring composition of the unexposed portion is removed to when the removal of the resist composition of the cured portion occurs is 60 seconds or more.

B: the time from when the coloring composition of the unexposed portion is removed until the resist composition of the cured portion is removed is 30 seconds or more and less than 60 seconds.

C: the time from when the coloring composition of the unexposed portion is removed until the resist composition of the cured portion is removed is less than 30 seconds.

(Formaldehyde detection amount)

0.5g of the coloring composition was poured into a Cartridge (manufactured by Waters, Sep Pak (registered trademark)) filled with Silica gel impregnated with DNPH (2, 4-dinitrophenylhydrazine), and allowed to stand at room temperature for 2 hours.

Elute with 4mL acetonitrile and bring to volume of 5 mL. The measurement was carried out using a liquid chromatograph (trade name: LC-10AD, manufactured by Shimadzu corporation, column: Pro C18 RS (4.6X 250mm, 5 μm, manufactured by YMC Co., Ltd.), mobile phase: a solution of acetonitrile/ultrapure water 65: 35, column temperature: 40 ℃, flow rate: 1.0 mL/min, detection wavelength: 360nm), using a mixed standard solution of two types of aldehyde-DNPH (0.1. mu.g aldehyde/. mu.L acetonitrile, manufactured by Wako pure chemical industries, Ltd.) as a standard. The amount of formaldehyde was calculated from the measurement results.

(amine number)

The amine number represents the mass of potassium hydroxide (KOH) equivalent to the alkali component equivalent of 1g of the solid content. The measurement sample was dissolved in tetrahydrofuran, and the resulting solution was neutralized and titrated with a 0.1 mol/L hydrochloric acid/2-propanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi chemical corporation). The inflection point of the titration pH curve was used as the titration end point, and the amine value (B) was calculated according to the following formula.

B＝56.11×Vs×0.1×f/w

B: amine number (mgKOH/g)

Vs: the amount of 0.1 mole/L hydrochloric acid/2-propanol solution required for titration (mL)

f: titre of 0.1 mol/L hydrochloric acid (2-propanol property)

w: measurement of sample Mass (g) (solid content conversion value)

(acid value)

The acid value represents the mass of potassium hydroxide required to neutralize an acid component corresponding to 1g of the solid component. Dissolving a sample to be measured in tetrahydrofuran, adding a plurality of drops of phenolphthalein ethanol solution as an indicator, and carrying out neutralization titration by using 0.1 mol/L potassium hydroxide/ethanol solution. The acid value (A) was calculated according to the following formula.

A＝56.11×Vs×0.1×f/w

A: acid value (mgKOH/g)

Vs: the amount of 0.1 mol/L KOH/ethanol solution (mL) required for titration

f: titre of 0.1 mol/L KOH/ethanol solution

w: measurement of sample Mass (g) (solid content conversion value)

< preparation of pigment Dispersion base liquid >

(pigment Dispersion base liquids No.1 to 12, 14 to 16)

The materials were mixed in the proportions shown in Table 1, and the mixture was kneaded by a bead mill for a whole day and night to prepare a pigment dispersion base liquid. The pigment dispersion base liquids Nos. 1 to 12 and 14 to 16 were all excellent in dispersion stability.

(preparation of pigment Dispersion base liquid No. 13)

The materials shown in table 1 except for the phosphite were mixed together, and after kneading with a bead mill for one day and night, the phosphite was added to the kneaded mixture to prepare a pigment dispersion base liquid. The pigment dispersion base liquid No.13 was good in dispersion stability.

TABLE 1

TABLE 2

The materials used in tables 1 and 2 are as follows.

SB 250: carbon Black (product of Cambot corporation, trade name "Special Black 250")

PY 185: c.i. pigment yellow 185

PV 29: c.i. pigment violet 29

PB 60: c.i. pigment blue 60

Dispersant 1: amino group-containing polyurethane resin type dispersant (acid value 0mgKOH/g, amine value 36mgKOH/g)

Dispersant 2: amino group-containing polyurethane resin type dispersant (acid value 0mgKOH/g, amine value 45mgKOH/g)

Dispersant 3: amino group-containing (meth) acrylic resin type dispersant (acid value: 0mgKOH/g, amine value: 63mgKOH/g)

Dispersant 4: amino group-containing polyester amide resin type dispersant (acid value 17mgKOH/g, amine value 10mgKOH/g)

Phthalocyanine (pigment derivative having copper phthalocyanine pigment skeleton, product name "Solsperse (registered trademark) 5000", manufactured by Luborun)

Alkali-soluble resin: benzyl methacrylate/methacrylic acid copolymer, acid value of 100mgKOH/g, amine value of 0mgKOH/g, weight average molecular weight of 30,000

TEP: phosphorous acid triethyl ester

TIDP: phosphorous acid triisodecyl ester

BBC: 4, 4' -Butylenebis (6-tert-butyl-o-cresol)

PGMEA: propylene glycol monomethyl ether acetate

< preparation of coloring composition Nos. 1 to 16 >

The pigment dispersion base liquids were uniformly mixed with the other materials in the ratios shown in tables 3 and 4 using a high-speed mixer. Then, the mixture was filtered through a filter having a pore diameter of 3 μm to obtain each colored composition.

TABLE 3

TABLE 4

The materials used in tables 3 and 4 are as follows.

A polymerizable compound: dipentaerythritol hexaacrylate

Irgacure 907: 2-methyl- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one manufactured by Ciba Specialty Chemicals

The evaluation results of the obtained coloring compositions are shown in tables 3 and 4. The coloring compositions Nos. 1 to 13 and 16 contain a coloring material, a dispersant, a dispersion medium and a specific phosphite. These coloring compositions Nos. 1 to 13 and 16 were all excellent in dispersion stability, developability and development latitude, and the detected amount of formaldehyde was reduced to 2ppm or less. Particularly, the coloring compositions Nos. 1 to 13 containing the phenolic antioxidant are more excellent in dispersion stability. Further, the timings of adding the phosphites in the coloring compositions No.2 and No.13 were different, and a comparison thereof revealed that the formaldehyde detection amount was further decreased when the phosphite was added in mixing the coloring material and the dispersant.

The present invention includes the following embodiments.

Embodiment 1 is a coloring composition for a black matrix, which contains a coloring material, a dispersant, a dispersion medium, and a phosphite ester, wherein the phosphite ester is a compound represented by general formula 5.

Embodiment 2A coloring composition for a black matrix according to embodiment 1, wherein the content of the phosphite is 0.1 to 100 parts by mass based on 100 parts by mass of the dispersant.

Embodiment 3 the coloring composition for a black matrix according to embodiment 1 or 2, wherein the dispersant is a resin-type dispersant having an amine value.

(embodiment 4) the coloring composition for a black matrix according to any one of embodiments 1 to 3, wherein the coloring composition further contains a phenol antioxidant.

Embodiment 5 the coloring composition for a black matrix according to embodiment 4, wherein the phenol antioxidant is a compound represented by general formula (6).

(embodiment 6) the coloring composition for a black matrix according to embodiment 4 or 5, wherein the content of the phenolic antioxidant is 0.1 to 25 parts by mass with respect to 100 parts by mass of the dispersant.

Embodiment 7A coloring composition for a black matrix according to any one of embodiments 1 to 6, wherein the coloring composition further contains a binder resin.

(embodiment 8) the coloring composition for a black matrix according to any one of embodiments 1 to 7, wherein the coloring composition contains a black pigment as a coloring material or contains two or more pigments other than the black pigment as a coloring material.

(embodiment 9) the color composition for a black matrix according to embodiment 3, wherein the amine value of the dispersant is 10mgKOH/g to 200 mgKOH/g.

(embodiment 10) the coloring composition for a black matrix according to any one of embodiments 1 to 9, wherein an acid value of the dispersant is less than 20 mgKOH/g.

(embodiment 11) the coloring composition for a black matrix according to any one of embodiments 1 to 10, wherein a total content of the coloring material is 10 to 80% by mass in a total solid content of the coloring composition.

(embodiment 12) the coloring composition for a black matrix according to any one of embodiments 1 to 11, wherein a content of the dispersant is 1 to 200 parts by mass with respect to 100 parts by mass of the coloring material.

(embodiment 13) the coloring composition for a black matrix according to any one of embodiments 1 to 12, wherein an optical density of a black resist pattern formed of the coloring composition and having a film thickness of 1 μm is 0.5 or more.

(embodiment 14) a color filter comprising a transparent substrate and a black matrix formed on the transparent substrate, wherein the black matrix is formed from the colored composition for a black matrix according to any one of embodiments 1 to 13.

Claims

1. A coloring composition for a black matrix, comprising a coloring material, a dispersant, a dispersion medium and a phosphite ester, wherein the phosphite ester is a compound represented by the general formula (5):

2. The coloring composition for a black matrix according to claim 1, wherein a content of the phosphite is 0.1 to 100 parts by mass with respect to 100 parts by mass of the dispersant.

3. The coloring composition for a black matrix according to claim 1 or 2, wherein the dispersant is a resin-type dispersant having an amine value.

4. The coloring composition for a black matrix according to any one of claims 1 to 3, further comprising a phenol antioxidant.

5. The coloring composition for a black matrix according to claim 4, wherein the phenol antioxidant is a compound represented by general formula (6):

6. The coloring composition for a black matrix according to claim 4 or 5, wherein the content of the phenolic antioxidant is 0.1 to 25 parts by mass with respect to 100 parts by mass of the dispersant.

7. The coloring composition for a black matrix according to any one of claims 1 to 6, further comprising a binder resin.

8. The coloring composition for a black matrix according to any one of claims 1 to 7, wherein the coloring composition contains a black pigment as a coloring material or contains a pigment other than two or more black pigments as a coloring material.

9. A color filter comprising a transparent substrate and a black matrix formed on the transparent substrate, wherein the black matrix is formed from the coloring composition for a black matrix according to any one of claims 1 to 8.