JP7308700B2 - Coloring composition for black matrix and color filter - Google Patents

Description

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

A color filter used in an image display device such as a liquid crystal display includes color pixels formed on a transparent substrate, which transmit light of the three primary colors of red (R), green (G), and blue (B), and boundaries between the color pixels. and a black matrix which is black and substantially does not transmit visible light.

In manufacturing 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 orienting the liquid crystal in a certain direction is formed thereon. In order to obtain sufficient performance of these transparent electrodes and alignment films, it is necessary to form them at a high temperature of 200° C. or higher. Therefore, as a method of applying a colorant to the transparent substrate of the color filter, a pigment dispersion method using a pigment having excellent heat resistance and light resistance as the colorant is widely used.

In the pigment dispersion method, a coloring composition in which a pigment, a dispersant, a binder resin and a dispersion medium (solvent) are mixed is used. When forming a colored layer, the colored composition is first applied to a transparent substrate to form a coating film of the colored composition on the transparent substrate. Next, radiation is applied (hereinafter referred to as “exposure”) through a photomask having a desired pattern to cure the binder resin. Finally, the unexposed portion is removed by development to form a colored layer having a desired pattern. Incidentally, the colored layer is subjected to a treatment such as heating as necessary. A color filter can be manufactured by forming a black pattern (hereinafter referred to as a "black matrix") and color pixels of red (R), green (G) and blue (B).

The black matrix is required to be formed in a lattice or band shape, to be a thin film, to have fine details, and to have sharp edges and high linearity. In recent years, a colored composition containing carbon black as a light-shielding material has been used to form a black matrix. In order to maintain a high light-shielding property with a thin film, it is necessary to increase the content concentration of carbon black. When carbon black is dispersed in a coloring composition, there is a problem in that as the surface area of carbon black increases, reaggregation tends to occur, resulting in a decrease in dispersion stability.

In order to solve this problem, there is a method of improving the affinity between the dispersing medium and carbon black in the coloring composition, and various dispersing agents have been investigated as a means for this. For example, a colored composition using a urethane-based dispersant (see Patent Document 1), a colored composition using a urethane-based dispersant having a basic functional group (see Patent Document 2), a polyester having a basic functional group, or A coloring composition using a polyether dispersant has been proposed (see Patent Document 3).

JP-A-2000-227654 JP 2009-175613 A JP-A-10-82908

In recent years, environmental standards have become stricter, and in the black matrix, formaldehyde generated over time due to the coloring composition has become a problem. For example, in conventional coloring compositions, the amount of formaldehyde in the coloring composition does not meet environmental standards.

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

The black matrix coloring composition of the present invention, which has solved the above problems, contains a coloring agent, a dispersant, a dispersion medium and a phosphite ester, and the phosphite ester is represented by the general formula (5) It is characterized by being a compound represented by

［一般式（５）において、Ｒ⁵¹は炭素数１～２０のアルキル基を表す。Ｒ⁵²およびＲ⁵³は、それぞれ独立して、炭化水素基を表す。Ｒ⁵²およびＲ⁵³は、互いに結合して環状構造を形成していてもよい。一般式（５）で表される化合物は、Ｒ⁵²またはＲ⁵³で結合して２量体または３量体を形成していてもよい。］

[In general formula (5), R ⁵¹ represents an alkyl group having 1 to 20 carbon atoms. ^R52 and ^R53 each independently represent a hydrocarbon group. R ⁵² and R ⁵³ may combine with each other to form a cyclic structure. The compound represented by general formula (5) may be bound at R ⁵² or R ⁵³ to form a dimer or trimer. ]

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

ADVANTAGE OF THE INVENTION According to this invention, the coloring composition for black matrices with high dispersibility of a coloring material and little formaldehyde generation|occurrence|production with time is obtained.

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

<Coloring composition for black matrix>
The coloring composition for black matrix of the present invention (hereinafter sometimes simply referred to as "coloring composition") contains a coloring agent, a dispersant, a dispersion medium and a phosphite, and the phosphite is , which is a compound represented by the general formula (5).

Conventional coloring compositions generate formaldehyde over time due to ingredients in the coloring composition. Here, in the coexistence of the phosphite represented by the general formula (5), the formaldehyde generated from the compounding agent reacts irreversibly with the phosphite. Therefore, formaldehyde in the coloring composition can be reduced.

The black matrix coloring composition preferably does not substantially transmit visible light. Specifically, the optical density (OD value) of the black resist pattern formed from the coloring composition is preferably 0.5 or higher, more preferably 1.0 or higher, and still more preferably 1.5 or higher. The optical density was measured by applying the colored composition on a glass substrate with a spin coater to a film thickness of 1 μm, forming a black resist pattern only in the solid portion, and measuring the black resist pattern with a Macbeth densitometer (TD- 931, manufactured by Macbeth).

Various components of the coloring composition for black matrix of the present invention are described below.

[Colorant]
As the coloring agent, any known coloring agent can be used without any particular limitation as long as it can give the coloring composition a black or pseudo-black hue. Here, the “pseudo-blackened hue” is ideally black, but any hue that is permitted as a black matrix used for the color filter of the liquid crystal display element may be used. The black matrix is basically required to be achromatic so as not to add extra color. Furthermore, if light leaks from the black matrix, the contrast of the image is lowered. Therefore, as described above, black is ideal in terms of absorbing all the light of each color. However, it does not have to be completely achromatic, as long as the hue does not add extra color to the image. It is included in the range of hues.

Examples of the coloring material include black pigments, mixed color pigments, mixtures thereof, and the like.

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

Examples of the mixed color pigment include those obtained by mixing two or more kinds of pigments other than black pigments to produce a pseudo-black color. As the mixed color pigment, two or more organic pigments selected from the group consisting of a blue organic pigment, a purple organic pigment, a yellow organic pigment, a red organic pigment and an orange organic pigment are mixed to produce a pseudo-black color. things are mentioned.

As a blue organic pigment, C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 22, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 64, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. be done.
As a purple organic pigment, C.I. I. pigment violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49, 50 and the like.
Examples of yellow organic pigments include C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,125,126,127,127:1,128,129,133,134, 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, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 213 and the like.
Examples of red organic pigments include C.I. 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, 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, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 97, 101, 101:1, 104, 108, 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, 269, 270, 271, 272, 273, 274, 275, 276 and the like.
As an orange organic pigment, C.I. 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 organic pigments selected from violet, yellow, red, and orange organic pigments is preferable.

The coloring material may contain a pigment derivative as a dispersing aid. As the dye derivative, it is preferable to contain a dye derivative having an acidic group. This dye derivative has an acidic functional group introduced into the dye skeleton. Specific examples of the dye skeleton include an azo dye skeleton, a phthalocyanine dye skeleton, an anthraquinone dye skeleton, a triazine dye skeleton, an acridine dye skeleton, and a perylene dye skeleton. A carboxy group, a phosphoric acid group, and a sulfonic acid group are preferable as the acidic group to be introduced into the dye skeleton. A sulfonic acid group is preferred for convenience of synthesis and strong acidity. The acidic group may be directly bonded to the dye skeleton, or may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, ether, sulfonamide or urethane bond.

The total content of the coloring materials in the coloring composition is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more in the total solid content of the coloring composition, and 80% by mass The following is preferable, more preferably 70% by mass or less, and still more preferably 60% by mass or less. Here, the solid content is a component other than the dispersion medium, which will be described later, in the coloring composition.

[Dispersant]
The coloring composition contains a dispersant. The dispersant has a site that has the property of adsorbing to the coloring material and a site that has affinity with the dispersion medium. The dispersant has a function of adsorbing to the coloring material and stabilizing the dispersion in the dispersion medium. The dispersant is not particularly limited, and may be appropriately selected according to the types of the coloring material and dispersion medium. As the dispersant, a resin-type dispersant that is used in a coloring composition for color filters can be used. Polyallylamine-based resin-type dispersants, carbodiimide-based resin-type dispersants, and the like are included.

Examples of the resin type dispersant include the following.
(1) from the group consisting of polyesters, polyamides and polyesteramides having amino groups and/or imino groups of polyamine compounds (e.g., polyallylamine, polyvinylamine, polyalkyleneamines such as polyethylenepolyimine) and free carboxy groups; A reaction product with at least one selected.
(2) A carbodiimide compound having at least one side chain selected from the group consisting of polyester side chains, polyether side chains and polyacrylic side chains and at least one basic nitrogen-containing group in the molecule. .
(3) Reaction products of amino compounds such as polyalkyleneimines and methyliminobispropylamines with polyesters having free carboxyl groups.
(4) Polyesters having one hydroxyl group such as alcohols such as methoxypolyethylene glycol and caprolactone polyesters, compounds having 2 to 3 isocyanate group-reactive functional groups, and isocyanate group reactivity in the isocyanate group of the polyisocyanate compound A reaction product obtained by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound having a functional group and a tertiary amino group.
(5) A reaction product obtained by reacting an acrylate polymer having an alcoholic hydroxyl group with a polyisocyanate compound and a hydrocarbon compound having an amino group.
(6) A reaction product obtained by adding a polyether chain to an amino compound.
(7) A reaction product obtained by reacting a compound having an isocyanate group with a compound having an amino group.
(8) 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.
(9) A reaction product of a polycarbonate compound having a functional group capable of reacting with an amino group at one end and a polyamine compound.
(10) selected from (meth)acrylic esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, stearyl (meth)acrylate, and benzyl (meth)acrylate; at least one, (meth)acrylamide, N-methylolamide, vinylimidazole, vinylpyridine, at least one basic group-containing polymerizable monomer such as a monomer having an amino group and a polycaprolactone skeleton, styrene, a styrene derivative, A copolymer with at least one other polymerizable monomer.
(11) A (meth)acrylic block copolymer comprising a block having a basic group such as a tertiary amino group or a quaternary ammonium base and a block having no basic functional group.
(12) A compound obtained by Michael addition reaction of a polycarbonate compound to polyallylamine.
(13) A carbodiimide compound having at least one polybutadiene chain and at least one basic nitrogen-containing group.
(14) A carbodiimide compound having at least one side chain having an amide group and at least one basic nitrogen-containing group in the molecule.
(15) A polyurethane compound having a structural unit having an ethylene oxide chain and a propylene oxide chain and having an amino group quaternized with a quaternizing agent.
(16) Obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule with an active hydrogen group of a compound having an active hydrogen group in the molecule and a carbazole ring and/or an azobenzene skeleton. and a carbazole ring for the total of an isocyanate group derived from an isocyanate compound having an isocyanurate ring in the molecule of the compound, and a urethane bond and a urea bond generated by the reaction between the isocyanate group and the active hydrogen group. A compound in which the number of azobenzene skeletons is 15 to 85%.

Among these resin-type dispersants, basic group-containing urethane resin-type dispersants, basic group-containing polyester resin-type dispersants, and basic group-containing (meth)acrylic resin-type dispersants are more preferable, and amino group-containing dispersants. A urethane resin type dispersant, an amino group-containing polyester resin type dispersant, and an amino group-containing (meth)acrylic resin type dispersant are more preferable. In particular, a basic group-containing urethane resin type dispersant is preferable, and among these, a basic group (amino group)-containing urethane having at least one selected from the group consisting of a polyester chain, a polyether chain, and a polycarbonate chain. A resin type dispersant is preferred.

The resin type dispersant is preferably a resin (polymer) having a polar functional group. It is believed that the polar functional group has the function of adsorbing to the pigment and stabilizing its dispersion in the dispersion medium. The polar functional groups include primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, imino groups, amido groups, nitrogen-containing heterocyclic groups, carboxy groups, phosphoric acid groups, sulfonic acid groups, and the like. is mentioned. The polar functional group is preferably at least one selected from primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, imino groups, amido groups and nitrogen-containing heterocyclic groups.

As the resin-type dispersant, a polymer having an amine value and no acid value (a polymer having an amine value of more than 0 mgKOH/g and an acid value of 0 mgKOH/g), an acid value having an amine value Polymers that do not have an acid value of more than 0 mgKOH/g and an amine value of 0 mgKOH/g, polymers that have an amine value and an acid value (polymers that have an amine value and an acid value of more than 0 mgKOH/g), acid values and polymers with no amine value (polymers with amine and acid values of 0 mg KOH/g).

As the resin-type dispersant, a polymer having an amine value (a polymer having an amine value exceeding 0 mgKOH/g) is preferable. The amine value of the resin-type dispersant is preferably 10 mgKOH/g or more and 200 mgKOH/g or less. If the amine value is 10 mgKOH/g or more, the dispersion stabilizing effect is further improved, and if the amine value is 200 mgKOH/g or less, the solubility of the coloring composition in an alkaline developing solution is improved, and the pattern processability is improved. do. Moreover, the resin-type dispersant preferably has an acid value of 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, still more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more with respect to 100 parts by mass of the coloring material. It is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less.

[Dispersion medium]
The coloring composition contains a dispersing medium. The dispersion medium can be appropriately selected as long as it disperses or dissolves other components (solid content) constituting the coloring composition, does not react with these components, and has moderate volatility. Available. As the dispersion medium, for example, conventionally known organic solvents can be used, 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 monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-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, tripropylene glycol monomethyl ether and other glycol monoalkyl ethers; ethylene Glycol dialkyl ethers such as 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, dipropylene glycol dimethyl ether; 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, methoxypentyl 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 monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, etc. glycol alkyl ether acetates; glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, propyl ether , diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; acetone, methyl ethyl ketone, 2-heptanone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, Ketones such as methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone, methoxymethylpentanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol , diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, benzyl alcohol, diacetone alcohol monohydric or polyhydric alcohols; n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, Aliphatic hydrocarbons such as dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl; Aromatic hydrocarbons such as benzene, toluene, xylene and cumene; Amyl formate and ethyl 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 caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-methyl-3 -chain or cyclic esters such as butyl methoxypropionate, γ-butyrolactone, and ethyl 2-hydroxypropionate; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogens such as butyl chloride and amyl chloride hydrocarbons; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile;
From the viewpoint of the dispersibility of the coloring material, the solubility of the dispersant, the applicability of the coloring composition, and the like, the organic solvent includes diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene. Glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, amylformate, ethyl 2-hydroxypropionate, butyl 3-methyl-3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and the like are preferred. . Only one type of dispersion medium may be contained in the coloring composition, or a plurality of types may be used.

The content of the dispersion medium in the coloring composition is not particularly limited and can be adjusted as appropriate. The content of the dispersing medium in the coloring composition is usually 99% by mass or less. Moreover, the content of the dispersion medium in the coloring composition is preferably 50% by mass or more in consideration of the viscosity suitable for application of the coloring composition.

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

［一般式（５）において、Ｒ⁵¹は炭素数１～２０のアルキル基を表す。Ｒ⁵²およびＲ⁵³は、それぞれ独立して、炭化水素基を表す。Ｒ⁵²およびＲ⁵³は、互いに結合して環状構造を形成していてもよい。一般式（５）で表される化合物は、Ｒ⁵²またはＲ⁵³で結合して２量体または３量体を形成していてもよい。］

[In general formula (5), R ⁵¹ represents an alkyl group having 1 to 20 carbon atoms. ^R52 and ^R53 each independently represent a hydrocarbon group. R ⁵² and R ⁵³ may combine with each other to form a cyclic structure. The compound represented by general formula (5) may be bound at R ⁵² or R ⁵³ to form a dimer or trimer. ]

R ⁵¹ represents an alkyl group having 1 to 20 carbon atoms. Examples of alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group and octyl. group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, isoundecyl group, dodecyl group, isododecyl group, tridecyl group, isotridecyl group, tetradecyl group, isotetradecyl group, hexadecyl group, isohexadecyl group , octadecyl group, isooctadecyl group, eicosyl group and the like. Among these, an ethyl group, a butyl group and an isodecyl group are preferred.

The hydrocarbon group represented by R ⁵² or R ⁵³ includes an optionally substituted alkyl group and an optionally substituted aromatic group. The total carbon number of the optionally substituted alkyl group is preferably 1-20, more preferably 1-15. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, isoundecyl group, dodecyl group, isododecyl group, tridecyl group, isotridecyl group, tetradecyl group, isotetradecyl group, hexadecyl group, isohexadecyl group, octadecyl group, iso chain alkyl groups such as octadecyl group and eicosyl group; and cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, methylcyclopentyl group and methylcyclohexyl group. Examples of the aromatic group include phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, and butylphenyl. group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group and the like.

R ⁵² and R ⁵³ may combine with each other to form a cyclic structure. Examples of rings formed by combining R ²¹ to R ²³ include the following partial structures. Furthermore, the compound represented by general formula (5) may be bound at R ⁵² or R ⁵³ to form a dimer or trimer.

The phosphite represented by the general formula (5) includes a phosphite represented by the general formula (5-1) and/or a phosphite represented by the general formula (5-2). is preferred.

［一般式（５－１）において、Ｒ⁵¹は炭素数１～２０のアルキル基を表す。複数存在するＲ⁵¹は、それぞれ同一でも異なっていてもよい。］

[In general formula (5-1), R ⁵¹ represents an alkyl group having 1 to 20 carbon atoms. Multiple R ⁵¹ may be the same or different. ]

［一般式（５－１）において、Ｒ⁵¹は炭素数１～２０のアルキル基を表す。複数存在するＲ⁵¹は、それぞれ同一でも異なっていてもよい。］

[In general formula (5-1), R ⁵¹ represents an alkyl group having 1 to 20 carbon atoms. Multiple R ⁵¹ may be the same or different. ]

The phosphites represented by the general formula (5) include triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, Trialkyl phosphites such as trioctyl phosphate, triisooctyl phosphite, trinonyl phosphite, tridecyl phosphite, triisodecyl phosphite; octyldiphenyl phosphite, decyldiphenyl phosphite, diphenyl phosphite Alkyldiphenyl phosphites such as isodecyl, tridecyldiphenyl phosphite, hexadecyldiphenyl phosphite; 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro Dimers of phosphites such as [5,5]undecane, 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, etc. is mentioned. Among these, trialkyl phosphite is preferred, and triethyl phosphite, tributyl phosphite, and triisodecyl phosphite are more preferred.

The phosphite represented by the general formula (5) contained in the coloring composition may be of one kind or may be of a plurality of kinds.

The content of the phosphite ester represented by the general formula (5) in the coloring composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the dispersant. It is more 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, still more preferably 60 parts by mass or less, and particularly preferably 25 parts by mass or less. is.

When preparing the coloring composition, the phosphite ester may be added to the coloring agent and/or the dispersing agent before mixing the coloring agent and the dispersing agent, or the coloring agent and the dispersing agent are mixed. It may be added at that time, or it may be added to the mixture after mixing the colorant and the dispersant.

[Phenolic antioxidant]
The coloring composition of the present invention can contain a known phenolic antioxidant. By containing a phenol-based antioxidant, the amount of formaldehyde in the colored composition can be further reduced. The reason why the amount of formaldehyde can be reduced is considered to be that the oxidative deterioration of the phosphite ester can be suppressed. Further, by containing a phenol-based antioxidant, even when the coloring composition contains a large amount of binder resin, 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 becomes remarkable.

A phenolic antioxidant refers to an antioxidant having a compound having at least one hydroxy group on at least one benzene ring. Specifically, when the hydroxy 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 radical. Such a substituent that can exclude the molecule of, for example, a bulky substituent (for example, a substituent in which the carbon atom bonded to the benzene ring is a quaternary carbon atom (specific examples, t-butyl group, adamantyl group, etc.)) An antioxidant having a chemical structure having

A compound represented by the general formula (6) is preferable as the phenol-based antioxidant.

［一般式（６）において、Ｒ⁶¹は水素原子または炭素数１～８のアルキル基を表す。Ｒ⁶²は、水素原子または炭素数１～４のアルキル基を表す。Ｒ⁶³は、炭素数２～２０の炭化水素基のいずれか１以上の炭素原子をエステル基もしくはエーテル基で置換した基、または、炭素数１～２０の炭化水素基を表す。ｎは１～６の数を表す。ただし、Ｒ⁶¹のベンゼン環と結合する炭素原子が１級～３級炭素原子である。］

[In general formula (6), R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁶² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁶³ represents a hydrocarbon group of 2 to 20 carbon atoms in which one or more carbon atoms are substituted with an ester group or ether group, or a hydrocarbon group of 1 to 20 carbon atoms. n represents a number from 1 to 6; However, the carbon atom bonded to the benzene ring of R ⁶¹ is a primary to tertiary carbon atom. ]

R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group and octyl. group, isooctyl group, and the like. Among these, 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 still more preferable, since they have a large synergistic effect of antioxidant performance. In R ⁶¹ , the carbon atom bonded to the benzene ring is never a quaternary carbon atom, and groups such as tert-butyl groups are unsuitable as R ⁶¹ .

R ⁶² represents 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 methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and tert-butyl group, with methyl group being preferred.

R ⁶³ represents a hydrocarbon group of 2 to 20 carbon atoms in which one or more carbon atoms are substituted with an ester group or ether group, or a hydrocarbon group of 1 to 20 carbon atoms. Examples of hydrocarbon groups having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, isoundecyl group, dodecyl group, isododecyl group, tridecyl group, isotridecyl group, tetradecyl group, isotetradecyl group, hexadecyl group, isohexadecyl Alkyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, and octenyl groups; , nonenyl group, decenyl group, undecenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and other alkenyl groups; cinnamyl group, benzhydryl group, trityl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group, aryl groups such as a dodecylphenyl group; and cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a methylcyclopentyl group and a methylcyclohexyl group. Among these, an alkyl group is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. The above group is a group when the value of n in the general formula (6) is 1, and when the value of n is 2, it becomes a group obtained by removing one arbitrary hydrogen atom from the above group. If the value is 3, it becomes a group obtained by removing two arbitrary hydrogen atoms from the above group. The value of n represents a number from 1 to 6, preferably from 1 to 4, more preferably from 2 or 3, because of good performance as an antioxidant and good raw material conditions.

R ⁶³ may be a group obtained by substituting one or more carbon atoms of any of hydrocarbon groups having 2 to 20 carbon atoms with an ester group or an ether group. The group may have either one of an ester group and an ether group, or both, or a plurality of them. From the viewpoint of a synergistic effect with the phosphite ester, R ⁶³ is preferably a hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of the compound of general formula (6) include 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4′-butylidenebis(6-tert-butyl -m-cresol), bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)], bis[3-(3-tert-butyl-4 -hydroxy-5-methylphenylpropionic acid](2,4,8,10-tetraoxaspiro[5,5]undecane-3,9-diyl)bis(2,2-dimethyl-2,1-ethanediyl)) etc.

The phenolic antioxidant contained in the coloring composition may be of only one type, or may be of a plurality of types.

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

When preparing the coloring composition, the phenolic antioxidant may be added to the coloring agent and/or the dispersing agent before mixing the coloring agent and the dispersing agent, or the coloring agent and the dispersing agent may be mixed. It may be added at the time of mixing, or may be added to the mixture after mixing the colorant and the dispersant. The phenolic antioxidant is preferably added to the coloring agent and/or the dispersing agent before mixing the coloring agent and the dispersing agent.

[Binder resin]
The coloring composition of the present invention can contain a binder resin (excluding the dispersant). Examples of the binder resin include alkali-soluble resins and 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, etc.). , thermosetting resins, and thermoplastic resins. These can be used singly or in combination of two or more. Among these, alkali-soluble resins and/or polymerizable compounds are preferred.

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

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

(alkali-soluble resin)
As the alkali-soluble resin, any one that acts as a binder for the coloring material and is soluble in the developing solution used in the development processing step when producing the color filter, preferably in the alkaline developing solution. is not particularly limited. The alkali-soluble resin is preferably a resin having an acidic group such as a carboxyl group or a phenolic hydroxy group.

As the alkali-soluble resin, for example, for a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, at least a part of the epoxy group of the copolymer is unsaturated A resin obtained by adding a basic acid, or a resin obtained by adding a polybasic acid anhydride to at least part of the hydroxy groups generated by the addition reaction; a linear resin containing a carboxy group in the main chain; carboxy A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxy group portion of the group-containing resin; (meth)acrylic resin; epoxy (meth)acrylate resin having a carboxy group; More than one species can be mixed and used.

Specific examples of the alkali-soluble resin include an acidic group-containing unsaturated monomer component, styrene, methylstyrene, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl Acid group-containing copolymer obtained by radical polymerization of at least one monomer component selected from the group consisting of (meth)acrylate, methyl (meth)acrylate, polystyrene macromonomer, polymethyl (meth)acrylate macromonomer, etc. Coalescing resin etc. are mentioned. Examples of the acidic group-containing unsaturated monomer component include (meth)acrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, citraconic acid, citraconic anhydride, citraconic acid monoalkyl ester, sulfoethyl ( meth)acrylate, butyl (meth)acrylamide sulfonic acid, phosphoethyl (meth)acrylate and the like.

The alkali-soluble resin may have a radically polymerizable carbon-carbon double bond in its side chain. By having a double bond in the side chain, the photocurability of the colored composition according to the present invention is enhanced, so that resolution and adhesion can be further improved. Examples of methods for introducing radically polymerizable carbon-carbon double bonds to side chains include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p- ) A method of reacting a compound such as vinylbenzyl glycidyl ether with the 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, and preferably 200,000 or less, more preferably 100,000 or less. When the Mw of the alkali-soluble resin is 500 or more, the colored layer formed from the coloring composition has good heat resistance, film strength, and the like. It becomes even better.

The acid value of the alkali-soluble resin is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and preferably 300 mgKOH/g or less, more preferably 200 mgKOH/g or less. When the acid value of the alkali-soluble resin is 10 mgKOH/g or more, the alkali developability when the coloring composition is used as a colored layer is further improved, and when it is 300 mgKOH/g or less, the film strength and the like are improved. Also, the amine value of the alkali-soluble resin is preferably less than 10 mgKOH/g.

In the coloring composition, the content of the alkali-soluble resin is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 30 parts by mass or more with respect to 100 parts by mass of the coloring material, and 200 parts by mass. The following is preferable, and 120 parts by mass or less is more preferable. 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, more preferably 5% by mass or more, and 70% by mass or less in the total solid content of the coloring composition is preferred, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

(Polymerizable compound)
As the polymerizable resin as the polymerizable compound, a (meth) A resin into which a crosslinkable group such as an acrylic compound or cinnamic acid is introduced is used. Linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymers and α-olefin-maleic anhydride copolymers are halved with (meth)acrylic compounds having hydroxyl groups such as hydroxyalkyl (meth)acrylates. Esterified polymers are also used.

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

Examples of the monomer having two or more polymerizable unsaturated bonds in the molecule as the polymerizable compound include bisphenol A di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butylene glycol 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 ) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta (Meth)acrylate and the like.

The content of the polymerizable compound in the coloring composition, in the total solid content of the coloring composition, is preferably 3 mass% or more, more preferably 5 mass% or more, preferably 50 mass% or less, more preferably 20 % by mass or less. 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 alkaline developability of the colored composition of the present invention is reduced, and scumming, film residue, etc. tend to occur easily on the substrate or light-shielding layer in the unexposed area. be.

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

[Photoinitiator]
The coloring composition preferably contains a photopolymerization initiator. Thereby, radiation sensitivity can be imparted to the coloring composition. The photopolymerization initiator is a compound that generates active species capable of initiating polymerization of the cross-linking agent upon exposure to radiation such as visible light, ultraviolet rays, far infrared rays, electron beams, and X-rays.

Examples of the photopolymerization initiator include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyloxime-based compounds, onium salt-based compounds, benzoin-based compounds, benzophenone-based compounds, and α-diketones. type compounds, polynuclear quinone-based compounds, diazo-based compounds, imidosulfonate-based compounds, aminoketone-based compounds, and the like. A photoinitiator can be used individually or in mixture of 2 or more types.

In the coloring composition of the present invention, the content of the photopolymerization initiator is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 20% by mass or less in the total solid content of the coloring composition. , more preferably 10% by mass or less. In this case, if the content of the photopolymerization initiator is too low, curing by exposure may be insufficient.

[Other compounds]
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 compounds, Acid anhydrides, pH adjusters, antioxidants other than the phenolic antioxidants, ultraviolet absorbers, light stabilizers, preservatives, anti-mold agents, anti-aggregation agents, adhesion improvers, development improvers, storage stability agent etc. can be mentioned.

[Method for producing colored composition]
The coloring composition includes a coloring agent, a dispersant, a dispersion medium, a phosphite ester, and, if necessary, a phenolic antioxidant, a binder resin, a photopolymerization initiator, a light diffusing agent (precipitable barium sulfate, etc.), It can be prepared by mixing other ingredients. For mixing, for example, a mixing and dispersing machine such as a paint shaker, bead mill, ball mill, dissolver or kneader can be used. The coloring composition is preferably filtered after mixing. The method of mixing each material is not particularly limited. For example, a method of mixing all materials at once; a method of mixing a coloring agent, a dispersant, and a dispersion medium; A method of mixing other materials into a liquid; a method of mixing a coloring agent, a dispersing agent, and a part of other materials to prepare a coloring agent-dispersed base, and then mixing other materials into this coloring agent-dispersed base; mentioned. The coloring composition has excellent dispersibility and suppresses generation of formaldehyde, so that it can be suitably used for a black matrix.

<Color filter>
The color filter of the present invention comprises, on a transparent substrate, color pixels that transmit light of the three primary colors of red (R), green (G) and blue (B), and a black matrix formed from the coloring composition. It is.

Examples of methods for manufacturing color filters include the following methods. Thermosetting resin sheets such as thermoplastic resin sheets such as polyester resin, polyolefin resin, polycarbonate resin and polymethyl methacrylate resin, epoxy resin, unsaturated polyester resin and poly(meth)acrylic resin, various types of glass For example, the black matrix coloring composition of the present invention is coated on a transparent substrate such as the above, and then prebaked to evaporate the solvent (dispersion medium) to form a coating film. Next, after exposing this coating film through a photomask, it is developed using an alkaline developer (such as an aqueous solution containing an organic solvent or a surfactant and an alkaline compound) to dissolve and remove the unexposed areas of the coating film. Sushi forms a black pattern (black matrix). Then, after post-baking if necessary, the same operation is sequentially repeated for red (R), green (G) and blue (B), so that a pixel array of three primary colors of red, green and blue is arranged on the substrate. A colored filter is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

When the coloring composition is applied to the substrate, an appropriate coating method such as a spray method, roll coating method, spin coating method (spin coating method), slit die coating method, bar coating method, etc. can be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

After forming a protective film on the thus obtained pixel pattern as necessary, a transparent conductive film (such as ITO) is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to form a color filter.

Since the color filter of the present invention suppresses the generation of formaldehyde and has high dimensional accuracy, it can be suitably used for color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like. can.

Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is by no means limited to the following examples, and can be modified as appropriate without changing the gist of the invention.

<Evaluation method>
(dispersion stability)
Each pigment dispersion base and coloring composition were put into a glass bottle, sealed, and stored at room temperature for 7 days. Each pigment dispersion base and coloring composition after storage were visually observed and evaluated according to the following evaluation criteria.
A: Neither thickening nor sedimentation is observed.
B: Increased viscosity and sediment to the extent that they return to the original state when lightly shaken are observed.
C: Viscosity and sedimentation to the extent that they do not recover even if shaken strongly are observed.

(Developability of resist pattern)
Each coloring composition was applied on a glass substrate with a spin coater to a thickness of 1 μm, and prebaked at 100° C. for 3 minutes. After that, using a mask capable of obtaining a grid pattern with a line width of 25 μm and an area ratio of the cured portion to the uncured portion of 20:80, exposure was performed with a UV integrated light quantity of 400 mJ/cm ² using a high-pressure mercury lamp. The coating film obtained was developed using a 0.05% potassium hydroxide aqueous solution, and the developability was evaluated according to the following evaluation criteria from the time required to remove the colored composition from the unexposed areas.
A: Can be completely removed within 30 seconds.
B: Can be completely removed within 60 seconds exceeding 30 seconds.
C: Not completely removed even after 60 seconds.

(Development margin of resist pattern)
Each coloring composition was applied on a glass substrate with a spin coater to a thickness of 1 μm, and prebaked at 100° C. for 3 minutes. After that, using a mask capable of obtaining a grid pattern with a line width of 25 μm and an area ratio of the cured portion to the uncured portion of 20:80, exposure was performed with a UV integrated light quantity of 400 mJ/cm ² using a high-pressure mercury lamp. The resulting coating film was developed using a 0.05% potassium hydroxide aqueous solution, and the time from when the colored composition in the unexposed portion was removed until the resist composition in the cured portion was removed. The development margin was evaluated according to the following evaluation criteria.
A: The time from when the colored composition in the unexposed portion was removed until the resist composition in the cured portion was removed was 60 seconds or longer.
B: The time from when the colored composition in the unexposed portion was removed until the resist composition in the cured portion was removed was 30 seconds or more and less than 60 seconds.
C: The time from when the colored composition in the unexposed portion was removed until the resist composition in the cured portion was removed was less than 30 seconds.

(Amount of formaldehyde detected)
Inject 0.5 g of the coloring composition into a cartridge (manufactured by Waters, Sep Pak (registered trademark) DNPH Silica Plus Cartridge (product number: WAT037500)) filled with silica gel impregnated with DNPH (2,4-dinitrophenylhydrazine). and allowed to stand at room temperature for 2 hours.
It was washed out with 4 mL of acetonitrile and diluted to 5 mL. Liquid chromatograph (manufactured by Shimadzu Corporation, trade name: LC-10AD, column: Pro C18 RS (4.6 × 250 mm, 5 μm (manufactured by YMC), mobile phase: acetonitrile / ultrapure water = 65:35 solution, column temperature : 40 ° C., flow rate: 1.0 mL / min, detection wavelength: 360 nm), using two types of aldehyde-DNPH mixed standard solution (0.1 μg aldehyde / μL acetonitrile, manufactured by Wako Pure Chemical Industries) as a standard substance, measurement The amount of formaldehyde was calculated from the measurement results.

(amine value)
The amine number represents the mass of potassium hydroxide (KOH) equivalent to the basic component per gram of solid content. A 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). Using the inflection point of the titration pH curve as the titration end point, the amine value (B) was calculated by the following equation.
B = 56.11 x Vs x 0.1 x f/w
B: amine value (mgKOH/g)
Vs: Amount (mL) of 0.1 mol/L hydrochloric acid/2-propanol solution required for titration
f: 0.1 mol/L hydrochloric acid (2-propanolic) titer w: Mass (g) of measurement sample (in terms of solid content)

(acid number)
The acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content. A measurement sample was dissolved in tetrahydrofuran, several drops of a phenolphthalein ethanol solution were added as an indicator, and neutralization titration was carried out with a 0.1 mol/L potassium hydroxide/ethanol solution. The acid value (A) was calculated by the following formula.
A = 56.11 x Vs x 0.1 x f/w
A: Acid value (mgKOH/g)
Vs: Amount (mL) of 0.1 mol/L potassium hydroxide/ethanol solution required for titration
f: Potency of 0.1 mol/L potassium hydroxide/ethanol solution w: Mass (g) of measurement sample (in terms of solid content)

<Preparation of pigment dispersion base>
(Pigment dispersion base No. 1-12, 14-16)
Various materials were collectively mixed so as to have the composition shown in Table 1, and kneaded overnight in a bead mill to prepare a pigment dispersion base. Pigment Dispersion Base No. All of 1 to 12 and 14 to 16 had good dispersion stability.

(Preparation of pigment dispersion base No. 13)
The materials shown in Table 1, except for the phosphite ester, were collectively mixed and kneaded overnight in a bead mill, and then the phosphite ester was added to the kneaded product to prepare a pigment dispersion base. Pigment Dispersion Base No. No. 13 had good dispersion stability.

Materials used in Tables 1 and 2 are as follows.
SB250: Carbon black (manufactured by Cabot, trade name “Special Black 250”)
PY185: C.I. I. pigment yellow 185
PV29: C.I. I. pigment violet 29
PB60: C.I. I. pigment blue 60
Dispersant 1: amino group-containing polyurethane resin type dispersant (acid value 0 mgKOH/g, amine value 36 mgKOH/g)
Dispersant 2: Amino group-containing polyurethane resin type dispersant (acid value 0 mgKOH/g, amine value 45 mgKOH/g)
Dispersant 3: Amino group-containing (meth) acrylic resin type dispersant (acid value 0 mgKOH/g, amine value 63 mgKOH/g)
Dispersant 4: amino group-containing polyester amide resin type dispersant (acid value 17 mgKOH/g, amine value 10 mgKOH/g)
Phthalocyanine-based (dye derivative having a copper phthalocyanine-based dye skeleton, manufactured by Lubrizol, trade name “Solsperse (registered trademark) 5000”)
Alkali-soluble resin: benzyl methacrylate/methacrylic acid copolymer, acid value 100 mgKOH/g, amine value 0 mgKOH/g, weight average molecular weight 30,000
TEP: triethyl phosphite TIDP: triisodecyl phosphite BBC: 4,4'-butylidenebis(6-t-butyl-m-cresol)
PGMEA (propylene glycol monomethyl ether acetate)

<Coloring composition No. Preparation of 1 to 16>
Using a high-speed stirrer, each pigment dispersion base and other materials were uniformly mixed so as to have the compositions shown in Tables 3 and 4. Then, each colored composition was obtained by filtering through a filter having a pore size of 3 μm.

Materials used in Tables 3 and 4 are as follows.
Polymerizable compound: Dipentaerythritol hexaacrylate Irgacure 907: 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one manufactured by Ciba Specialty Chemicals

Tables 3 and 4 show the evaluation results of the obtained colored compositions. Coloring composition no. 1 to 13, 16 are cases where a coloring agent, a dispersing agent, a dispersing medium and a specific phosphite ester are contained. These coloring compositions no. 1 to 13 and 16 had good dispersion stability, developability, and development margin, and the amount of formaldehyde detected was reduced to 2 ppm or less. In particular, coloring composition No. 1 containing a phenolic antioxidant. 1 to 13 were even more excellent in dispersion stability. Moreover, coloring composition No. 2 and 13 differ in the timing of addition of the phosphite ester, but from these comparisons, the addition of the phosphite ester when mixing the coloring material and the dispersant further reduces the amount of formaldehyde detected. rice field.

Claims (9)

containing a coloring agent, a dispersant, a dispersing medium and a phosphite,
A coloring composition for a black matrix, wherein the phosphite is a compound represented by the general formula (5-1) .

[In general formula (5-1), R ⁵¹ represents an alkyl group having 1 to 20 carbon atoms. Multiple R ⁵¹ may be the same or different. ] 2. The coloring composition for black matrix according to claim 1, wherein the content of said phosphite ester is 0.1 parts by mass to 100 parts by mass with respect to 100 parts by mass of said dispersant. 3. The coloring composition for black matrix according to claim 1, wherein the dispersant is a resin-type dispersant having an amine value. The black matrix coloring composition according to any one of claims 1 to 3, further comprising a phenolic antioxidant. The coloring composition for black matrix according to claim 4, wherein the phenolic antioxidant is a compound represented by the general formula (6).

[In general formula (6), R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁶² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁶³ represents a hydrocarbon group of 2 to 20 carbon atoms in which one or more carbon atoms are substituted with an ester group or ether group, or a hydrocarbon group of 1 to 20 carbon atoms. n represents a number from 1 to 6; However, the carbon atoms bonded to the benzene ring of R ⁶¹ are primary to tertiary carbon atoms. ] 6. The coloring composition for black matrix according to claim 4, wherein the content of said phenolic antioxidant is 0.1 to 25 parts by mass with respect to 100 parts by mass of said dispersant. The black matrix coloring composition according to any one of claims 1 to 6, further comprising a binder resin. The black matrix coloring composition according to any one of claims 1 to 7, wherein the black matrix coloring composition contains a black pigment as a coloring material, or contains two or more pigments other than a black pigment. Composition. comprising a transparent substrate and a black matrix formed on the transparent substrate;
A color filter, wherein the black matrix is formed from the coloring composition for a black matrix according to any one of claims 1 to 8.