WO2021044860A1 - Coloring composition for black matrix, and color filter - Google Patents

Abstract

[Problem] To provide a coloring composition which is for a black matrix, and has high dispersion performance of a coloring material and a small amount of formaldehyde generated over time. [Solution] This coloring composition for a black matrix is characterized by containing a coloring material, a dispersant, a dispersion medium, and phosphite, wherein the phosphite is a compound represented by general formula (5). [In general formula (5), R51 represents a C1-C20 alkyl group. R52 and R53 each independently represent a hydrocarbon group. R52 and R53 may be bonded to each other to form a cyclic structure. The compounds represented by general formula (5) may be bonded to each other at R52 or R53 to form a dimer or a trimer.]

Description

Coloring compositions and color filters for black matrix

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

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

In the manufacture of liquid crystal displays, a transparent electrode for driving a 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 on the transparent electrode. 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 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 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, and a coating film made of the colored composition is formed on the transparent substrate. Next, the binder resin is cured by irradiating 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 having a desired pattern shape. The colored layer is subjected to a treatment such as heating as necessary. Then, a color filter can be manufactured by forming a black pattern (hereinafter referred to as "black matrix") and color pixels of red (R), green (G), and blue (B).

The black matrix is formed in a grid pattern or a band shape, is a thin film and details, and is required to have sharp edges 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 a high light-shielding property in a thin film, it is necessary to increase the content concentration of carbon black. When carbon black is dispersed in the coloring composition, there is a problem that reaggregation is likely to occur as the surface area of carbon black increases, and the dispersion stability is lowered.

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

Japanese Unexamined Patent Publication No. 2000-227654 JP-A-2009-175613 Japanese Unexamined Patent Publication No. 10-82908

In recent years, environmental standards have become stricter, and formaldehyde generated over time due to the coloring composition has become a problem in the black matrix. For example, in the conventional coloring compositions such as Patent Documents 1 to 3, the amount of formaldehyde in the coloring composition does not meet the environmental standard.

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 dispersion performance of a coloring material and a small amount of formaldehyde generated over time.

The coloring composition for a black matrix of the present invention, which has been able to solve the above problems, contains a coloring material, 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 represented compound.

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

By coexisting the phosphite ester represented by the general formula (5) in the coloring composition, formaldehyde generated from the compounding agent reacts irreversibly with the phosphite ester to reduce formaldehyde in the coloring composition. it can.

According to the present invention, it is possible to obtain a coloring composition for a black matrix, which has high dispersion performance of a coloring material and a small amount of formaldehyde generated over time.

Hereinafter, an example of a preferable embodiment of the present invention will be described. However, the following embodiments are merely examples. It is not limited to the following embodiments. In the present invention, "(meth) acrylic" refers to "at least one of acrylic and methacrylic". "(Meta) acrylate" refers to "at least one of acrylate and methacrylate".

<Coloring composition for black matrix>
The coloring composition for a black matrix of the present invention (hereinafter, may be simply referred to as “coloring composition”) contains a coloring material, a dispersant, a dispersion medium and a phosphite ester, and the phosphite ester is , It is a compound represented by the general formula (5).

In the conventional coloring composition, formaldehyde is generated over time due to the compounding agent in the coloring composition. Here, by coexisting the phosphite ester represented by the general formula (5), formaldehyde generated from the compounding agent reacts irreversibly with the phosphite ester. Therefore, formaldehyde in the coloring composition can be reduced.

It is preferable that the coloring composition for black matrix 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 more, more preferably 1.0 or more, still more preferably 1.5 or more. For the optical density, the coloring composition was applied onto a glass substrate with a spin coater so as to have a film thickness of 1 μm, and a black resist pattern was formed only on the solid portion. Regarding this black resist pattern, a Macbeth densitometer (TD- Measured using 931, manufactured by Macbeth.

Various components and the like of the coloring composition for black matrix of the present invention will be described below.

[Coloring material]
As the coloring material, a known coloring material can be used without particular limitation as long as the coloring composition can have a black or pseudo-black hue. Here, the "pseudo-blackened hue" is ideally black, but any hue that is acceptable as a black matrix used in the color filter of the liquid crystal display element may be used. The black matrix basically needs to be achromatic so as not to add extra color. Further, when light leaks from the black matrix, the contrast of the image is lowered. Therefore, black is ideal as described above in that it absorbs all the light of each color. However, it does not have to be completely achromatic, as long as it is in the range of hues that do not add extra color to the image, and the hues that can absorb the light required to maintain contrast are pseudo-blackened. It is included in the hue range.

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

Examples of the black pigment include carbon black, graphite, perylene pigment, lactam pigment, titanium black, metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, and composite oxides. , Metal sulfide, metal sulfate, metal carbonate and the like. Among these, carbon black and titanium black are preferable from the viewpoint of shading rate and image characteristics. Examples of the carbon black include furnace black, channel black, acetylene black, thermal black, lamp black, and bone black. Further, as the carbon black, either neutral carbon black or acidic carbon black can be used, and these may be used in combination. The hue of the black pigment is not limited to black, which is an achromatic color in terms of 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 the black pigment to make them pseudo-black. As the color mixing pigment, two or more kinds of organic pigments selected from the group consisting of blue organic pigments, purple organic pigments, yellow organic pigments, red organic pigments and orange organic pigments were mixed and pseudo-blackened. Things can be mentioned.

Examples of the blue organic pigment include 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 and the like. Be done.
Examples of purple organic pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49, 50 and the like can be mentioned.
Examples of the yellow organic pigment 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 can be mentioned.
Examples of the red organic pigment 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.
Examples of the orange organic pigment include 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 can be mentioned.

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

The coloring material may contain a dye derivative as a dispersion aid. The dye derivative preferably contains a dye derivative having an acidic group. This dye derivative has an acidic functional group introduced into the dye skeleton. Specific examples of the pigment skeleton include an azo pigment skeleton, a phthalocyanine pigment skeleton, an anthraquinone pigment skeleton, a triazine pigment skeleton, an aclysin pigment skeleton, and a perylene pigment skeleton. As the acidic group introduced into the dye skeleton, a carboxy group, a phosphoric acid group and a sulfonic acid group are preferable. A sulfonic acid group is preferable for convenience of synthesis and strength of 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, an ether, a sulfonamide, 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, still more preferably 30% by mass or more, and 80% by mass, based on the total solid content of the coloring composition. The following is preferable, more preferably 70% by mass or less, still more preferably 60% by mass or less. Here, the solid content is a component in the coloring composition other than the dispersion medium described later.

[Dispersant]
The coloring composition contains a dispersant. The dispersant has a portion having a property of adsorbing to the coloring material and a moiety having an affinity with the dispersion medium. The dispersant has a function of adsorbing on a coloring material and stabilizing dispersion in a dispersion medium. The dispersant is not particularly limited, and may be appropriately selected depending on the type of the colorant and the dispersion medium. As the dispersant, the resin-type dispersant used in the coloring composition for a color filter can be used. For example, a polyester-based resin-type dispersant, a (meth) acrylic-based resin-type dispersant, a polyurethane-based resin-type dispersant, and the like. Examples thereof include polyallylamine-based resin-type dispersants and carbodiimide-based resin-type dispersants.

Examples of the resin type dispersant include the following.
(1) From the group consisting of an amino group and / or an imino group of a polyamine compound (for example, polyalkyleneamine such as polyallylamine, polyvinylamine, polyethylene polyimine) and polyester, polyamide and polyesteramide having a free carboxy group. Reaction product with at least one selected.
(2) A carbodiimide-based 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 at least one basic nitrogen-containing group in the molecule. ..
(3) A reaction product of an amino compound such as polyalkyleneimine or methyliminobispropylamine and a polyester having a free carboxy group.
(4) Polyisocyanate compounds such as alcohols such as methoxypolyisocyanate glycol and polyesters having one hydroxyl group such as caprolactone polyester, compounds having 2 to 3 isocyanate group reactive functional groups, and isocyanate group reactive. A reaction product obtained by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound having a functional group and a tertiary amino group.
(5) A reaction product obtained by reacting a polymer of an acrylate having an alcoholic hydroxyl group with a polyisocyanate compound and a hydrocarbon compound having an amino group.
(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 carboxy 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 acid 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 kind, at least one kind of basic group-containing polymerizable monomer such as (meth) acrylamide, N-methylolamide, vinyl imidazole, vinylpyridine, a monomer having an amino group and a polycaprolactone skeleton, and a styrene, a styrene derivative, A copolymer with at least one of other polymerizable monomers.
(11) A (meth) acrylic block copolymer composed of a block having a basic group such as a tertiary amino group and a quaternary ammonium base and a block having no basic functional group.
(12) A compound obtained by carrying out a Michael addition reaction of a polycarbonate compound with polyallylamine.
(13) A carbodiimide-based compound having at least one polybutadiene chain and one basic nitrogen-containing group.
(14) A carbodiimide-based 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 by a quaternizing agent.
(16) Obtained by reacting the isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule with the active hydrogen group of a compound having an active hydrogen group in the molecule and having a carbazole ring and / or an azobenzene skeleton. The carbazole ring with respect to the total of the isocyanate group derived from the isocyanate compound having an isocyanurate ring in the molecule of the compound, and the urethane bond and urea bond generated by the reaction of the isocyanate group and the active hydrogen group. A compound having an azobenzene skeleton of 15-85%.

Among these resin-type dispersants, a basic group-containing urethane-based resin-type dispersant, a basic group-containing polyester-based resin-type dispersant, and a basic group-containing (meth) acrylic resin-type dispersant are more preferable, and an amino group-containing dispersant is preferable. Urethane-based resin-type dispersants, amino group-containing polyester-based resin-type dispersants, and amino group-containing (meth) acrylic-based resin-type dispersants 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-based dispersant is preferable.

The resin type dispersant is preferably a resin (polymer) having a polar functional group. It is considered that the polar functional group has a function of adsorbing to the pigment and stabilizing the 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 base, an imino group, an amide group, a nitrogen-containing heterocyclic group, a carboxy group, a phosphoric acid group and a sulfonic acid group. Can be mentioned. As the polar functional group, at least one selected from a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, an imino group, an amide group and a nitrogen-containing heterocyclic group is preferable.

The resin-type dispersant includes 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), and a polymer having an acid value and having an amine value. Non-polymer (polymer with acid value over 0 mgKOH / g and amine value over 0 mgKOH / g), polymer with amine value and acid value (polymer with amine value and acid value over 0 mgKOH / g), acid value And there are polymers that do not have an amine value (polymers with an amine value and acid value of 0 mgKOH / g).

As the resin type dispersant, a polymer having an amine value (a polymer having an amine value of more than 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. When the amine value is 10 mgKOH / g or more, the dispersion stabilizing effect is further improved, and when the amine value is 200 mgKOH / g or less, the solubility of the coloring composition in the alkaline developing solution is good and the pattern processability is improved. To do. Further, 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 further preferably 50 parts by mass or less.

[Dispersed medium]
The coloring composition contains a dispersion medium. The dispersion medium is appropriately selected as long as it disperses or dissolves other components (solids) constituting the coloring composition, does not react with these components, and has appropriate volatility. Can be used. As the dispersion medium, for example, a conventionally known organic solvent can be used, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether. , Propropylene 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, glycol monoalkyl ethers such as tripropylene glycol monomethyl ether; ethylene Glycoldialkyl 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. Glycolalkyl Ether acetates; Glycoldiacetates 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, dihexyl ether and other ethers; acetone, methyl ethyl ketone, 2-heptanone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone. , Cyclohexanone, ethylamyl ketone, methylbutyl ketone, methylhexyl ketone, methylnonyl ketone, methoxymethylpentanone and other ketones; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, Monovalent or polyhydric alcohols such as dipropylene glycol, triethylene glycol, glycerin, benzyl alcohol, diacetone alcohol; n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane, etc. Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; amylformate, ethylformate, ethyl acetate , Butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprilate, 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-methoxypropion Chain or cyclic esters such as butyl acid, γ-butyrolactone, ethyl 2-hydroxypropionate; alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid; halogens such as butyl chloride and amilk loride Hydrocarbons; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile.
The organic solvent contains diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene from the viewpoints of dispersibility of the coloring material and the like, solubility of the dispersant, and coatability of the coloring composition. 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 preferable. .. The dispersion medium contained in the coloring composition may be only one type or may be a plurality of types.

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

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

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

R ⁵¹ represents 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 and an octyl group. 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, eikosyl group and the like. Among these, an ethyl group, a butyl group and an isodecyl group are preferable.

Examples of the hydrocarbon group represented by R ⁵² or R ⁵³ 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 the substituent is preferably 1 to 20, more preferably 1 to 15. Examples of the alkyl group 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. 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, Octadecil group, Iso Chain-like alkyl groups such as octadecyl group and eicosyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, methylcyclopentyl group and methylcyclohexyl group can be mentioned. Examples of the aromatic group include a phenyl group, a toluyl group, a xylyl group, a cumenyl 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 and a butylphenyl group. Examples thereof include a 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.

R ⁵² and R ⁵³ may be coupled to each other to form a cyclic structure. Examples of the ring formed by connecting R ⁵² and R ⁵³ to each other include the following partial structures. Further, the compound represented by the general formula (5) may be ^{bonded by R 52} or R ⁵³ to form a dimer or a trimer.

The phosphite ester represented by the general formula (5) includes a phosphite ester represented by the general formula (5-1) and / or a phosphite ester represented by the general formula (5-2). Is preferable.

[In the general formula (5-1), R ⁵¹ represents an alkyl group having 1 to 20 carbon atoms. A plurality of R ^51s may be the same or different from each other. ]

[In the general formula (5-2), R ⁵¹ represents an alkyl group having 1 to 20 carbon atoms. A plurality of R ^51s may be the same or different from each other. ]

Examples of the phosphite ester represented by the general formula (5) include triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, trypentyl phosphite, trihexyl phosphite, and sub-phosphate. Trialkyl phosphites such as trioctyl phosphate, triisooctyl phosphite, trinonyl phosphite, tridecyl phosphite, triisodecyl phosphite; octyldiphenyl phosphite, decyldiphenyl phosphite, diphenyl phosphite Alkyl phosphite esters such as isodecyl, tridecyldiphenyl phosphite, hexadecyldiphenyl phosphate; 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] Undecane, 3,9-bis (isodecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] Dimeric of phosphite ester such as undecane, etc. Can be mentioned. Among these, trialkyl phosphite is preferable, and triethyl phosphite, tributyl phosphate, and triisodecyl phosphite are more preferable.

The phosphite ester represented by the general formula (5) contained in the coloring composition may be of only one type or of a plurality of types.

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, based on 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.

At the time of preparation of the coloring composition, the phosphite ester may be added to the coloring material and / or the dispersant before mixing the coloring material and the dispersant, or the coloring material and the dispersant are mixed. It may be added at the time, or it may be added to this 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 phenolic antioxidant, the amount of formaldehyde in the coloring 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 phenolic antioxidant, the dispersion stability of the coloring material can be improved even when the coloring composition contains a large amount of binder resin. 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 is 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-position, 4-position and 6-position, or at least one of the 3-position, 4-position and 6-position has a radical. Substituents that can eliminate the molecule of, for example, bulky substituents (eg, substituents in which the carbon atom bonded to the benzene ring is a quaternary carbon atom (specific example, t-butyl group, adamantyl group, etc.)) An antioxidant having a chemical structure having a

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

[In the 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 group in which any one or more carbon atoms of the 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. 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 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 and an octyl group. Groups, isooctyl groups and the like can be mentioned. 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 further preferable, because the synergistic effect of the antioxidant performance is large. In R ^61, the carbon atom bonded to the benzene ring does not become a quaternary carbon atom, and for example, a group such as a tert-butyl group is not suitable for 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 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.

R ⁶³ represents a group in which any one or more carbon atoms of the 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 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 and an 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 groups, octadecyl groups, isooctadecyl groups, eicosyl groups; vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, isobutenyl groups, pentenyl groups, isopentenyl groups, hexenyl groups, heptenyl groups, octenyl groups. , Nonenyl group, decenyl group, undecenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and other alkenyl groups; phenyl group, toluyl group, xsilyl group, cumenyl group, mesityl group, benzyl group, phenethyl group, styryl group, Synamyl 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 dodecylphenyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, methylcyclopentyl group and methylcyclohexyl group can be mentioned. 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 is 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 of 1 to 6, but the number of 1 to 4 is preferable, and the number of 2 or 3 is more preferable because the performance as an antioxidant is good and the raw material conditions are good.

R ⁶³ may be a group in which one or more carbon atoms of any of the hydrocarbon groups having 2 to 20 carbon atoms are substituted with an ester group or an ether group. The group may have only one of an ester group and an ether group, a group having both, or a group having a plurality of the groups. From the viewpoint of 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 the general formula (6) include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 4,4'-butylidenebis (6-tert-butyl). -M-cresol), bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylene bis (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)) And so on.

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

In the coloring composition, the content of the phenolic antioxidant is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more with respect to 100 parts by mass of the dispersant. It 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.

At the time of preparation of the coloring composition, the phenolic antioxidant may be added to the colorant and / or the dispersant before mixing the colorant and the dispersant, or the colorant and the dispersant may be mixed. It may be added at the time of preparation, or it may be added to this mixture after mixing the colorant and the dispersant. The phenolic antioxidant is preferably added to the colorant and / or the dispersant before mixing the colorant and the dispersant.

[Binder resin]
The coloring composition of the present invention can contain a binder resin (however, the dispersant is excluded). 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 resin, thermoplastic resin and the like. These can be used alone or in combination of two or more. Among these, alkali-soluble resins and / or polymerizable compounds are preferable.

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 resins used, and is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass, based on the total solid content of the coloring composition. As described above, it is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.

(Alkali-soluble resin)
The alkali-soluble resin may be one that acts as a binder for the coloring material and is soluble in a developing solution, preferably an alkali developing solution, that is used in the developing process when producing a color filter. For example, it is not particularly limited. The alkali-soluble resin is preferably a resin having an acidic group such as a carboxy group or a phenolic hydroxy group.

The alkali-soluble resin includes, for example, a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, which is unsaturated in at least a part of the epoxy groups of the copolymer. A resin to which a basic acid is added, or a resin obtained by adding a polybasic acid anhydride to at least a part of hydroxy groups generated by the addition reaction; a linear resin having a carboxy group in the main chain; carboxy Resins to which an epoxy group-containing unsaturated compound is added to the carboxy group portion of the group-containing resin; (meth) acrylic resin; epoxy (meth) acrylate resin having a carboxy group and the like can be mentioned, and these can be used alone or 2 Seeds and above 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, and benzyl. Acid group-containing common weight 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 and the like. Combined resin and the like can be 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, and sulfoethyl. Examples thereof include meta) acrylate, butyl (meth) acrylamide sulfonic acid, and phosphoethyl (meth) acrylate.

The alkali-soluble resin may have a carbon-carbon double bond capable of radical polymerization in the side chain. By having a double bond in the side chain, the photocurability of the coloring composition according to the present invention is enhanced, so that the resolution and adhesion can be further improved. Examples of the method for introducing a radically polymerizable carbon-carbon double bond into the side chain 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 can be mentioned.

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 and film strength of the colored layer formed from the coloring composition are good, and when the Mw is 200,000 or less, the alkali developability of this coating film is high. It will be even better.

The acid value of the alkali-soluble resin is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, preferably 300 mgKOH / g or less, and 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. 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, and 200 parts by mass with respect to 100 parts by mass of the coloring material. The following is preferable, and more preferably 120 parts by mass or less. 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, still more preferably 5% by mass or more, and 70% by mass or less, based on the total solid content of the coloring composition. Is preferable, more preferably 60% by mass or less, still more preferably 50% by mass or less.

(Polymerizable compound)
The polymerizable resin as the polymerizable compound is a linear polymer having a reactive substituent such as a hydroxy group, a carboxy group or an amino group via an isocyanate group, an aldehyde group, an epoxy group or the like (meth). A resin having a crosslinkable group such as an acrylic compound or silicic acid introduced therein is used. A linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is halved with a (meth) acrylic compound having a hydroxy group such as a hydroxyalkyl (meth) acrylate. Eesterated copolymers are also used.

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

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

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, based on the total solid content of the coloring composition. It is less than mass%. 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 coloring composition of the present invention tends to have low alkali developability, and background stains, film residues, etc. tend to occur on the substrate or the light-shielding layer in the unexposed portion. is there.

(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, and polyvinyl acetate. Polyurethane resin, phenol resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, celluloses, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin And so on.

[Photopolymerization initiator]
The coloring composition preferably contains a photopolymerization initiator. Thereby, the coloring composition can be imparted with radiation sensitivity. The photopolymerization initiator is a compound that generates an active species capable of initiating the polymerization of a cross-linking agent by 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. Examples thereof include system compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, aminoketone compounds and the like. The photopolymerization initiator may be used alone or in combination of two or more.

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 amount of the solid matter of the coloring composition. , More preferably 10% by mass or less. In this case, if the content of the photopolymerization initiator is too small, curing may be insufficient due to exposure, while if it is too large, the formed colored layer tends to easily fall off from the substrate during development.

[Other combinations]
Other compounding agents include sensitizers, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, plasticizers, organic carboxylic acid compounds, and organic carboxylic acids. Acid anhydrides, pH adjusters, antioxidants other than the phenolic antioxidants, UV absorbers, light stabilizers, preservatives, antifungal agents, anti-aggregation agents, adhesion improvers, development improvers, storage stability Agents and the like can be mentioned.

[Manufacturing method of coloring composition]
The coloring composition includes a coloring material, a dispersant, a dispersion medium, a phosphite ester, a phenolic antioxidant, a binder resin, a photopolymerization initiator, a photodiffusing agent (precipitated barium sulfate, etc.), if necessary. It can be prepared by mixing other compounding agents. For mixing, for example, a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, and a kneader can be used. The coloring composition is preferably filtered after mixing. The method of mixing each material is not particularly limited, and for example, a method of mixing all the materials at once; a colorant, a dispersant, and a dispersion medium are mixed, the colorant is dispersed in advance, and then the colorant is dispersed. A method of mixing other materials in a liquid; a method of mixing a colorant, a dispersant, and a part of other materials to prepare a colorant dispersion base, and then mixing other materials with the colorant dispersion base, etc. Can be mentioned. Since the coloring composition has excellent dispersibility and suppresses the generation of formaldehyde, it can be suitably used for a black matrix.

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

Examples of the method for manufacturing the color filter include the following methods. First, sheets made of thermoplastic resins such as polyester resins, polyolefin resins, polycarbonate resins, and polymethylmethacrylate resins, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly (meth) acrylic resins, and various glasses. For example, the coloring composition for black matrix of the present invention is applied onto a transparent substrate such as, and then prebaked to evaporate the solvent (dispersion medium) to form a coating film. Next, the coating film is exposed to a photomask and then developed with an alkaline developer (an aqueous solution containing an organic solvent or a surfactant and an alkaline compound, etc.) to dissolve and remove the unexposed portion of the coating film. And form a black pattern (black matrix). Then, after post-baking as necessary, the same operation is repeated sequentially for red (R), green (G), and blue (B), so that the pixel arrays of the three primary colors of red, green, and blue are arranged on the substrate. The resulting color filter is obtained. However, in the present invention, the order in which the pixels of each color are formed is not limited to the above.

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

A protective film is formed on the pixel pattern thus obtained as needed, and then a transparent conductive film (ITO (indium tin oxide) or the like) 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 and the like, it is suitably used for a color liquid crystal display element, a color image pickup tube element, a color sensor, an organic electroluminescence display element, electronic paper, and the like. Can be done.

Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples, and can be appropriately modified and implemented without changing the gist thereof.

<Evaluation method>
(Dispersion stability)
Each pigment dispersion base and coloring composition were taken in glass bottles, sealed tightly, and stored at room temperature for 7 days. Each pigment dispersion base and coloring composition after storage were visually confirmed and evaluated according to the following evaluation criteria.
A: No thickening or sediment is observed.
B: Thickening and sedimentation that returns to the original level when shaken lightly are observed.
C: Thickening and sediments that do not return to their original state even when shaken strongly are observed.

(Developability of resist pattern)
Each coloring composition was applied onto a glass substrate with a spin coater so as to have a film thickness of 1 μm, and prebaked at 100 ° C. for 3 minutes. Then, using a mask capable of obtaining a grid pattern having a line width of 25 μm in which the area ratio of the cured portion to the uncured portion was 20:80, exposure ^{was performed using a high-pressure mercury lamp with a UV integrated light intensity of 400 mJ / cm 2.} The coating film obtained by using a 0.05% potassium hydroxide aqueous solution was developed, and the developability was evaluated according to the following evaluation criteria from the time when the coloring composition of the unexposed portion could be removed.
A: It can be completely removed within 30 seconds.
B: It can be completely removed within 60 seconds over 30 seconds.
C: It cannot be completely removed even if it exceeds 60 seconds.

(Development margin of resist pattern)
Each coloring composition was applied onto a glass substrate with a spin coater so as to have a film thickness of 1 μm, and prebaked at 100 ° C. for 3 minutes. Then, using a mask capable of obtaining a grid pattern having a line width of 25 μm in which the area ratio of the cured portion to the uncured portion was 20:80, exposure ^{was performed using a high-pressure mercury lamp with a UV integrated light intensity of 400 mJ / cm 2.} The obtained coating film was developed using a 0.05% potassium hydroxide aqueous solution, and the time from the time when the coloring composition of the unexposed portion could be removed to the time when the resist composition of the cured portion was removed was taken. The measurement was performed and the development margin was evaluated according to the following evaluation criteria.
A: The time from when the coloring composition of the unexposed portion can be removed to the removal of the resist composition of the cured portion is 60 seconds or more.
B: The time from when the coloring composition of the unexposed portion can be removed to the removal of the resist composition of the cured portion is 30 seconds or more and less than 60 seconds.
C: The time from when the coloring composition of the unexposed portion can be removed to the removal of the resist composition of the cured portion is less than 30 seconds.

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

(Amine value)
The amine value represents the mass of the basic component and the equivalent amount of potassium hydroxide (KOH) per 1 g of solid content. The measurement sample was dissolved in tetrahydrofuran, and the obtained 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 amine value (B) was calculated by the following formula with the inflection point of the titration pH curve as the titration end point.
B = 56.11 × Vs × 0.1 × f / w
B: Amine value (mgKOH / g)
Vs: Amount of 0.1 mol / L hydrochloric acid / 2-propanol solution required for titration (mL)
f: Titer of 0.1 mol / L hydrochloric acid (2-propanol property) w: Mass (g) of measurement sample (in terms of solid content)

(Acid value)
The acid value represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of solid content. The measurement sample was dissolved in tetrahydrofuran, several drops of a phenolphthalein ethanol solution was added as an indicator, and the mixture was neutralized and titrated with a 0.1 mol / L potassium hydroxide / ethanol solution. The acid value (A) was calculated by the following formula.
A = 56.11 × Vs × 0.1 × f / w
A: Acid value (mgKOH / g)
Vs: Amount of 0.1 mol / L potassium hydroxide / ethanol solution required for titration (mL)
f: Titer 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 Nos. 1-12, 14-16)
Various materials were mixed all at once so as to have the composition shown in Table 1, and the meat was kneaded with a bead mill for 24 hours 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)
Each material excluding the phosphite ester shown in Table 1 was mixed all at once and kneaded with a bead mill for a whole day and night, and then the phosphite ester was added to the kneaded meat to prepare a pigment dispersion base. Pigment dispersion base No. No. 13 had good dispersion stability.

The 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 (pigment derivative having a copper phthalocyanine-based pigment skeleton, manufactured by Lubrizol, trade name "Solspace (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 phosphate 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.

The materials used in Tables 3 and 4 are as follows.
Polymerizable Compound: Dipentaerythritol Hexaacrylate Irgacure 907: Ciba Specialty Chemicals, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one

The evaluation results of the obtained coloring composition are shown in Tables 3 and 4. Coloring composition No. 1 to 13 and 16 are cases where a colorant, a dispersant, a dispersion medium and a specific phosphite ester are contained. These coloring compositions No. In Nos. 1 to 13 and 16, the dispersion stability, developability, and development margin were all good, and the amount of formaldehyde detected was reduced to 2 ppm or less. In particular, the coloring composition No. 1 containing a phenolic antioxidant. 1 to 13 had more excellent dispersion stability. In addition, the coloring composition No. Although the timing of addition of the phosphite ester is different between 2 and 13, the amount of formaldehyde detected is further reduced when the phosphite ester is added when the colorant and the dispersant are mixed. It was.

The present invention includes the following embodiments.
(Embodiment 1)
Contains colorants, dispersants, dispersion media and phosphite esters,
A coloring composition for a black matrix, wherein the phosphite ester is a compound represented by the general formula (5).

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

(Embodiment 2)
The coloring composition for a black matrix according to the first aspect, wherein the content of the phosphite ester is 0.1 part by mass to 100 parts by mass with respect to 100 parts by mass of the dispersant.

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

(Embodiment 4)
The black matrix coloring composition according to any one of aspects 1 to 3, wherein the coloring composition further contains a phenolic antioxidant.

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

[In the 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 group in which any one or more carbon atoms of the 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. 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.} ]

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

(Embodiment 7)
The black matrix coloring composition according to any one of aspects 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 aspects 1 to 7, wherein the coloring composition contains a black pigment as a coloring material, or contains two or more kinds of pigments other than the black pigment.

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

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

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

(Embodiment 12)
The coloring composition for a black matrix according to any one of aspects 1 to 11, wherein the content of the dispersant is 1 part by mass 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 aspects 1 to 12, wherein the black resist pattern having a film thickness of 1 μm formed from the coloring composition has an optical density of 0.5 or more.

(Embodiment 14)
A transparent substrate and a black matrix formed on the transparent substrate are provided.
A color filter characterized in that the black matrix is formed from the coloring composition for black matrix according to any one of aspects 1 to 13.

Claims (9)

1. Contains colorants, dispersants, dispersion media and phosphite esters,
   A coloring composition for a black matrix, wherein the phosphite ester is a compound represented by the general formula (5).
   

   

   [In the general formula (5), R ⁵¹ represents an alkyl group having 1 to 20 carbon atoms. R ⁵² and R ⁵³ each independently represent a hydrocarbon group. R ⁵² and R ⁵³ may be coupled to each other to form a cyclic structure. The compound represented by the general formula (5) may be ^{bonded at R 52} or R ⁵³ to form a dimer or a trimer. ]
2. The coloring composition for a black matrix according to claim 1, wherein the content of the phosphite ester is 0.1 part by mass 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, wherein the coloring composition further contains a phenolic antioxidant.
5. The coloring composition for a black matrix according to claim 4, wherein the phenolic antioxidant is a compound represented by the general formula (6).
   

   

   [In the 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 group in which any one or more carbon atoms of the 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. 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.} ]
6. The coloring composition for a black matrix according to claim 4 or 5, wherein the content of the phenolic antioxidant is 0.1 part by mass to 25 parts by mass with respect to 100 parts by mass of the dispersant.
7. The coloring composition for black matrix according to any one of claims 1 to 6, wherein the coloring composition further contains 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 two or more kinds of pigments other than the black pigment.
9. A transparent substrate and a black matrix formed on the transparent substrate are provided.
   A color filter characterized in that the black matrix is formed from the coloring composition for black matrix according to any one of claims 1 to 8.