JP2019171371A - Dispersant composition, coloring composition, and color filter - Google Patents

Abstract

To provide a dispersant composition which has high dispersion performance of a colorant, has a small temporal generation amount of formaldehyde, and is less in discoloration even when being exposed to high temperature.SOLUTION: A dispersion composition contains a resin type dispersant having a tertiary amino group and phosphorous ester, in which the phosphorous ester is a compound represented by formula (5). (In formula (5), Rrepresents an alkyl group having 1 to 20 carbon atoms; Rand Rmay form a cyclic structure; and the compound represented by formula (5) may form a dimer or a trimer.SELECTED DRAWING: None

Description

  The present invention relates to a dispersant composition containing a resin-type dispersant having a tertiary amino group.

  Conventionally, in the production of a color filter used for a liquid crystal display or the like, a dyeing method, a printing method, an ink jet method, an electrodeposition method, a pigment dispersion method, and the like are known as methods for applying a coloring material to a substrate. Among these, the pigment dispersion method is the mainstream from the viewpoints of spectral characteristics, durability, pattern shape, and accuracy. In this pigment dispersion method, a coating film made of a colored composition in which a pigment, a dispersant, a dispersion medium (solvent), a binder resin, and the like are mixed is formed on a substrate, and radiation is emitted through a photomask having a desired pattern shape. Irradiation is cured and alkali development is performed.

  In recent years, in order to obtain good color reproducibility and high contrast of a color filter, studies have been made on increasing the concentration of the pigment in the coloring composition. When the concentration of the pigment is increased, since the proportion of the dispersant is relatively reduced, the dispersant is required to have high dispersibility (see, for example, Patent Document 1 (paragraph 0004)). In alkali development, a binder resin having alkali solubility plays a major role. However, in the case of a pigment dispersion composition in which the concentration of the pigment is increased, the ratio of the binder resin that is a developing component decreases, and the alkali developability deteriorates. Therefore, the alkali developability originally required for the binder resin is also required for the dispersant. As such a dispersant, Patent Document 2 discloses, as a pigment dispersion, an AB block copolymer comprising an A block having a polylactone chain in the side chain and a B block having a tertiary amino group in the side chain. It is described that it is used (see Patent Document 2 (paragraphs 0023 to 0045)).

JP 2009-265515 A JP 2013-119568 A

  In the resin-type dispersant, it has been proposed to introduce a tertiary amino group into the side chain in order to enhance the dispersibility of the coloring material (see Patent Document 2). However, a resin-type dispersant having a tertiary amino group generates formaldehyde over time due to the tertiary amino group. Therefore, when such a resin-type dispersant is used for a colored composition, formaldehyde is contained in the colored composition. In recent years, environmental standards have become stricter. Therefore, when a conventional resin-type dispersant is used, the amount of formaldehyde in the coloring composition does not meet the environmental standards.

  In the production of a liquid crystal display, after forming the pattern shape of the colored layer, a transparent electrode for driving the liquid crystal is formed thereon by vapor deposition or sputtering, and further, the liquid crystal is oriented in a certain direction on the transparent electrode. An alignment film is formed. These transparent electrodes and alignment films are generally molded at a high temperature of 200 ° C. or higher in order to obtain sufficient performance. Here, the coloring composition using the resin-type dispersant having a tertiary amino group tends to be discolored in a process involving high heat. For this reason, there is a problem in that the luminance of the final color filter is adversely affected.

  The present invention has been made in view of the above circumstances, and provides a dispersant composition having a high colorant dispersion performance, a small amount of formaldehyde generated over time, and little discoloration even when exposed to high temperatures. For the purpose.

  The dispersant composition of the present invention that has been able to solve the above problems contains a resin-type dispersant having a tertiary amino group and a phosphite, wherein the phosphite is represented by the general formula (5). It is a compound represented.

［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. R ⁵² and R ⁵³ each independently represents a hydrocarbon group. R ⁵² and R ⁵³ may be bonded to each other to form a cyclic structure. The compound represented by the general formula (5) may be bonded with R ⁵² or R ⁵³ to form a dimer or trimer. ]

  A resin-type dispersant having a tertiary amino group generates formaldehyde over time due to the amino group. Further, when the resin type dispersant having a tertiary amino group is exposed to a high temperature, the tertiary amino group is oxidized and the resin type dispersant is yellowed. Here, by making the phosphite represented by the general formula (5) coexist, formaldehyde generated from the resin-type dispersant and the phosphite react irreversibly. Therefore, formaldehyde in the dispersant composition can be reduced. Moreover, the phosphite can suppress the oxidation of the tertiary amino group and can suppress the yellowing of the resin-type dispersant.

  The present invention also includes a coloring composition comprising the dispersant composition, a coloring material, a binder resin, and a dispersion medium. The present invention also includes a color filter comprising a colored layer formed using the colored composition.

  According to the present invention, it is possible to obtain a dispersant composition having a high colorant dispersion performance, a small amount of formaldehyde generated over time, and little discoloration even when exposed to high temperatures.

  Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiments are merely examples. It is not limited at all to the following embodiments.

<Dispersant composition>
The dispersant composition of the present invention contains a resinous dispersant having a tertiary amino group and a phosphite, and the phosphite is a compound represented by the general formula (5). And

  A resin-type dispersant having a tertiary amino group generates formaldehyde over time due to the amino group. Further, when the resin type dispersant having a tertiary amino group is exposed to a high temperature, the tertiary amino group is oxidized and the resin type dispersant is yellowed. Here, by making the phosphite represented by the general formula (5) coexist, formaldehyde generated from the resin-type dispersant and the phosphite react irreversibly. Therefore, formaldehyde in the dispersant composition can be reduced. Moreover, the phosphite can suppress the oxidation of the amino group and can suppress the yellowing of the resin-type dispersant.

  In the present invention, “(meth) acryl” means “at least one of acryl and methacryl”. “(Meth) acrylic monomer” refers to a monomer having a “(meth) acryloyl group” in the molecule. “(Meth) acryloyl” refers to “at least one of acryloyl and methacryloyl”. “Vinyl monomer” refers to a monomer having a carbon-carbon double bond capable of radical polymerization in the molecule. The “structural unit derived from a (meth) acrylic monomer” refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a (meth) acrylic monomer is polymerized into a carbon-carbon single bond. The “structural unit derived from a vinyl monomer” refers to a structural unit in which a carbon-carbon double bond capable of radical polymerization of a vinyl monomer is polymerized into a carbon-carbon single bond.

  Examples of the resin-type dispersant having a tertiary amino group include (meth) acrylic polymers, urethane polymers, polyester polymers, polyethyleneimine polymers, polyoxyethylene alkyl ether polymers, polyoxyethylene alkyls. Examples thereof include phenyl ether polymers.

  The amine value of the resin-type dispersant is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and still more preferably 30 mgKOH / g or more, from the viewpoint of adsorptivity to the colorant and colorant dispersibility. 200 mgKOH / g or less is preferable, More preferably, it is 150 mgKOH / g or less, More preferably, it is 100 mgKOH / g or less.

(Block copolymer)
From the viewpoint of dispersibility, the resin-type dispersant preferably has an A block having a structural unit derived from a (meth) acrylic monomer and a B block having a structural unit represented by the general formula (1). It is a block copolymer.

［一般式（１）において、Ｒ¹¹およびＲ¹²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を表す。Ｒ¹¹およびＲ¹²が互いに結合して環状構造を形成していてもよい。Ｘ¹は２価の連結基を表す。Ｒ¹³は水素原子またはメチル基を表す。］

[In General Formula (1), R ¹¹ and R ¹² each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹³ represents a hydrogen atom or a methyl group. ]

  Various components of the block copolymer will be described below.

(Block A)
The A block is a polymer block containing a structural unit derived from a (meth) acrylic monomer. The structural unit derived from the (meth) acrylic monomer in the A block may be only one type, or may have two or more types. By having the structural unit derived from the (meth) acrylic monomer, it is possible to maintain high affinity with the dispersion medium (solvent) and the binder resin blended in the coloring composition.

  The content of the structural unit derived from the (meth) acrylic monomer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, particularly preferably in 100% by mass of the A block. Is 100% by mass.

  The (meth) acryl monomer is a (meth) acrylate having a chain alkyl group (straight chain alkyl group or branched chain alkyl group), a (meth) acrylate having a cyclic alkyl group, or a (meth) acrylate having a polycyclic structure. , (Meth) acrylate having an aromatic group, (meth) acrylate having a polyalkylene glycol structural unit, (meth) acrylate having a hydroxy group, (meth) acrylate having a lactone-modified hydroxy group, (meth) having an alkoxy group Acrylate, (meth) acrylate having an oxygen-containing heterocyclic group, (meth) acrylate having an acidic group, (meth) acrylic acid, and the like can be used, and one or more of these can be used in combination. Can do.

  As the (meth) acrylate having a linear alkyl group, a (meth) acrylate having a linear alkyl group having 1 to 20 carbon atoms in the linear alkyl group is preferable, and the linear alkyl group having 1 to carbon atoms in the range of 1 to 20 carbon atoms. A (meth) acrylate having a linear alkyl group of 10 is more preferred. Examples of the (meth) acrylate having a linear alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, Examples include n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-lauryl (meth) acrylate, and n-stearyl (meth) acrylate.

  As the (meth) acrylate having a branched chain alkyl group, a (meth) acrylate having a branched chain alkyl group having 1 to 20 carbon atoms in the branched chain alkyl group is preferable, and the branched chain alkyl group having 1 to 1 carbon atoms. A (meth) acrylate having a branched alkyl group of 10 is preferred. Examples of the (meth) acrylate having a branched chain alkyl group include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isooctyl (meth) acrylate, 2- Examples include ethylhexyl (meth) acrylate, isononyl (meth) acrylate, and isodecyl (meth) acrylate.

  The (meth) acrylate having a cyclic alkyl group is preferably a (meth) acrylate having a cyclic alkyl group having 6 to 12 carbon atoms in the cyclic alkyl group. Examples of the cyclic alkyl group include a cyclic alkyl group having a monocyclic structure (for example, a cycloalkyl group). Specific examples of the (meth) acrylate having a monocyclic cyclic alkyl group include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, and the like.

  The (meth) acrylate having a polycyclic structure is preferably a (meth) acrylate having a polycyclic structure having 6 to 12 carbon atoms in the polycyclic structure. Examples of the polycyclic structure include cyclic alkyl groups having a bridged ring structure (eg, adamantyl group, norbornyl group, isobornyl group). Specific examples of the (meth) acrylate having a polycyclic structure include isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, 2-methyl-2-adamantyl (Meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, etc. are mentioned.

  The (meth) acrylate having an aromatic group is preferably a (meth) acrylate having an aromatic group having 6 to 12 carbon atoms in the aromatic group. Examples of the aromatic group include an aryl group and the like, and may have a chain portion such as an alkylaryl group, an aralkyl group, and an aryloxyalkyl group. Specific examples of the (meth) acrylate having an aromatic group include benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like.

  Examples of the (meth) acrylate having a polyalkylene glycol structural unit include polyethylene glycol (degree of polymerization = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization = 2 to 10) ethyl ether (meth) acrylate, polyethylene Glycol (polymerization degree = 2 to 10) propyl ether (meth) acrylate, polyethylene glycol (polymerization degree = 2 to 10) (meth) acrylate having a polyethylene glycol structural unit such as phenyl ether (meth) acrylate; polypropylene glycol (polymerization degree) = 2-10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 2-10) ethyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 2-10) propyl ether Ether (meth) acrylate, polypropylene glycol (polymerization degree = 2-10), and the (meth) acrylate having a polypropylene glycol structure unit such as a phenyl ether (meth) acrylate.

  Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6- Examples include hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate. Among these, (meth) acrylates having 1 to 5 carbon atoms and having a hydroxyalkyl group are more preferable.

  Examples of the (meth) acrylate having a lactone-modified hydroxy group include those obtained by adding a lactone to the (meth) acrylate having a hydroxy group, and those obtained by adding caprolactone are preferred. The addition amount of caprolactone is preferably 1 mol to 10 mol, and more preferably 1 mol to 5 mol. Examples of the (meth) acrylate having a lactone-modified hydroxy group include 2-hydroxyethyl (meth) acrylate caprolactone 1 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 2 mol adduct, 2-hydroxyethyl (meth) acrylate. A caprolactone 3 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 4 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 5 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 10 mol adduct and the like are preferable. .

  Examples of the (meth) acrylate having an alkoxy group include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like.

  The (meth) acrylate having an oxygen-containing heterocyclic group is preferably a (meth) acrylate having a 4-membered to 6-membered oxygen-containing heterocyclic group. Specific examples of the (meth) acrylate having an oxygen-containing heterocyclic group include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, (2- Methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2-[(2-tetrahydropyranyl) oxy] ethyl (meth) acrylate, 1,3-dioxane- (meth) acrylate and the like can be mentioned.

Examples of the acidic group include a carboxy group (—COOH), a sulfonic acid group (—SO ₃ H), a phosphoric acid group (—OPO ₃ H ₂ ), a phosphonic acid group (—PO ₃ H ₂ ), and a phosphinic acid group (— PO ₂ H ₂ ). Examples of the (meth) acrylate having an acidic group include (meth) acrylate having a carboxy group, (meth) acrylate having a phosphate group, and (meth) acrylate having a sulfone group.

  Examples of the (meth) acrylate having a carboxy group include carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, 2- Examples include monomers obtained by reacting (meth) acrylates having a hydroxy group such as (meth) acryloyloxyethyl phthalate with acid anhydrides such as maleic anhydride, succinic anhydride, and phthalic anhydride, and (meth) acrylic acid. Examples of the (meth) acrylate having a sulfonic acid group include ethyl sulfonate (meth) acrylate. Examples of the (meth) acrylate having a phosphoric acid group include 2- (phosphonooxy) ethyl (meth) acrylate.

  The A block may have a structural unit other than the structural unit derived from the (meth) acrylic monomer. The other structural unit that can be contained in the A block is not particularly limited as long as it is formed by a vinyl monomer that can be copolymerized with both a (meth) acrylic monomer and a vinyl monomer that forms the B block described later. Vinyl monomers that can form other structural units of the A block may be used alone or in combination of two or more.

  Specific examples of vinyl monomers that can form other structural units of the A block include α-olefins, aromatic vinyl monomers, vinyl monomers containing heterocycles, vinyl amides, vinyl carboxylates, dienes, and the like. These vinyl monomers may have a hydroxy group or an epoxy group.

Examples of the α-olefin include 1-hexene, 1-octene, 1-decene and the like.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene and the like.
Examples of the vinyl monomer containing a heterocycle include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 2-vinylpyridine, 4-vinylpyridine, N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, and the like. Can be mentioned.
Examples of the vinylamide include N-vinylformamide, N-vinylacetamide, 1-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam and the like.
Examples of vinyl carboxylate include vinyl acetate, vinyl pivalate, vinyl benzoate and the like.
Examples of dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and the like.

  The A block preferably contains a structural unit represented by the general formula (10), that is, a structural unit derived from the (meth) acrylate having the lactone-modified hydroxy group. Since the structural unit represented by the general formula (10) has an ester bond portion and a terminal hydroxy group in the side chain, it has high affinity with the dispersion medium and the binder resin, and the alkali developability of the block copolymer. To increase.

［式（１０）において、ｎ１は１〜１０の整数である。Ｒ¹は水素原子またはメチル基である。Ｒ²は炭素数が１〜１０のアルキレン基である。Ｒ³は炭素数が１〜１０のアルキレン基である。］

[In Formula (10), n1 is an integer of 1-10. R ¹ is a hydrogen atom or a methyl group. R ² is an alkylene group having 1 to 10 carbon atoms. R ³ is an alkylene group having 1 to 10 carbon atoms. ]

  N1 in the formula (10) is preferably an integer of 1 to 7, and more preferably an integer of 1 to 5.

The alkylene group having 1 to 10 carbon atoms represented by R ² may be linear or branched, but is preferably linear. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ² include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, Nonamethylene group, decamethylene group, 1-methylethylene group and the like can be mentioned. R ² is preferably an alkylene group having 1 to 5 carbon atoms.

The alkylene group having 1 to 10 carbon atoms represented by R ³ may be linear or branched, but is preferably linear. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ³ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, Nonamethylene group, decamethylene group, etc. are mentioned. R ³ is preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 3 to 8 carbon atoms.

  When the A block contains a structural unit represented by the general formula (10), the content is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably in 100% by mass of the A block. Is 30% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. By making the content rate of the structural unit derived from the (meth) acrylate having a lactone-modified hydroxy group within the above range, the alkali developability of the block copolymer can be enhanced.

  The A block preferably has a structural unit derived from a vinyl monomer having an acidic group (preferably (meth) acrylate or (meth) acrylic acid having an acidic group). By having a structural unit derived from a vinyl monomer having an acidic group, solubility in an alkali developer is increased, and alkali developability can be improved. However, when the ratio increases, the affinity with the solvent and the alkali-soluble resin may be lowered. Therefore, it is preferable that the ratio of the structural unit derived from the vinyl monomer having an acidic group is such that the total acid value of the block copolymer is lower than the amine value.

  When the structural unit derived from the vinyl monomer having an acidic group is contained, the content is preferably 2% by mass or more, more preferably 5% by mass or more, and further preferably 7% by mass or more in 100% by mass of the A block. 20 mass% or less is preferable, More preferably, it is 18 mass% or less, More preferably, it is 16 mass% or less. If the content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate when neutralized with an alkali is increased in alkali development, and if it is 20% by mass or less, the hydrophilicity is high. However, it is possible to prevent the formed pixels from becoming messy.

  In the A block, the content of the structural unit represented by the general formula (1) described later is less than 5% by mass, preferably 3% by mass or less, more preferably 1% by mass or less. More preferably, the structural unit represented is not contained. As the content of the structural unit represented by the general formula (1) in the A block is lower, the dispersion performance of the coloring material is improved.

  The A block preferably has no amino group. That is, it is preferable that the vinyl monomer constituting the A block does not contain a vinyl monomer having an amino group. When a large amount of amino groups are present in the A block, when used as a dispersant, the colorant is adsorbed by both the A block and the B block, and the dispersion performance of the colorant is deteriorated. The content of structural units derived from vinyl monomers having an amino group in the A block (including those in which the amino group is quaternized) is preferably 2% by mass or less, more preferably 1% by mass or less, More preferably, it is 0.1 mass% or less, Most preferably, it is 0 mass%.

  When two or more kinds of structural units are contained in the A block, various structural units contained in the A block may be contained in any form such as random copolymerization and block copolymerization in the A block. From the viewpoint of uniformity, it is preferably contained in the form of random copolymerization. For example, the A block may be formed of a copolymer of a structural unit composed of an a1 block and a structural unit composed of an a2 block.

(B block)
The B block is a polymer block containing a structural unit represented by the following general formula (1).

(Structural unit represented by general formula (1))
The structural unit represented by the general formula (1) may be only one type, or may have two or more types. By setting it as the structural unit represented by General formula (1), adsorptivity with a coloring material is high and heat resistance can be made high.

［一般式（１）において、Ｒ¹¹およびＲ¹²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を表す。Ｒ¹¹およびＲ¹²が互いに結合して環状構造を形成していてもよい。Ｘ¹は２価の連結基を表す。Ｒ¹³は水素原子またはメチル基を表す。］

[In General Formula (1), R ¹¹ and R ¹² each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹³ represents a hydrogen atom or a methyl group. ]

Examples of the chain hydrocarbon group represented by R ¹¹ and R ¹² include a linear alkyl group and a branched alkyl group. As carbon number of the said linear alkyl group, C1-C20 is preferable, C1-C10 is more preferable, and C1-C5 is further more preferable. Examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group and the like. Is mentioned. As carbon number of the said branched alkyl group, C3-C20 is preferable, C3-C10 is more preferable, C3-C5 is further more preferable. Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, neopentyl group, and isooctyl group.

Examples of the substituent of the chain hydrocarbon group represented by R ¹¹ and R ¹² include a halogen group, an alkoxy group, a benzoyl group (—COC ₆ H ₅ ), and a hydroxy group.

Examples of the cyclic hydrocarbon group represented by R ¹¹ and R ¹² include a cyclic alkyl group and an aromatic group, and the cyclic alkyl group and the aromatic group may have a chain portion. As carbon number of the said cyclic alkyl group, C4-C18 is preferable, C6-C12 is more preferable, C6-C10 is further more preferable. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. As carbon number of the said aromatic group, C6-C18 is preferable, C6-C12 is more preferable, and C6-C8 is further more preferable. Examples of the aromatic group include a phenyl group, a tolyl group, a xylyl group, and a mesityl group. Examples of the cyclic alkyl group having a chain portion and the chain portion of an aromatic group having a chain portion include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably carbon. Examples of the alkylene group include 1 to 3.

Examples of the substituent that the cyclic hydrocarbon group represented by R ¹¹ and R ¹² has include a halogen group, an alkoxy group, a chain alkyl group, and a hydroxy group.

Examples of the cyclic structure formed by combining R ¹¹ and R ¹² with each other include a 5-membered to 7-membered nitrogen-containing heterocycle or a condensed ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring. Specific examples include structures represented by the following formulas (1-1), (1-2), and (1-3).

［一般式（１−１）、（１−２）、（１−３）において、Ｒ¹⁴は、炭素数１〜６のアルキル基を示す。ｌは０〜５の整数を表す。ｍは０〜４の整数を表す。ｎは０〜４の整数を表す。＊は結合手を表す。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ¹⁴は、それぞれ同一でも異なっていてもよい。］

[In General Formulas (1-1), (1-2), and (1-3), R ¹⁴ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5; m represents an integer of 0 to 4. n represents an integer of 0 to 4. * Represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ¹⁴ may be the same or different. ]

In the general formula (1), examples of the divalent linking group X ¹ include an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH—R ¹⁵ — group (amide group), a —COO—R ¹⁶ — group. (ester group) and the like, preferably -CONH-R ¹⁵ - a group - groups and / or -COO-R ¹⁶ - a group, more preferably -COO-R ^16. The bonding direction of the amide group and the ester group is not particularly limited, but the bonding mode of the amide group is preferably C—CO—NH—R ¹⁵ —NR ¹¹ R ¹² , and the bonding mode of the ester group is C—CO —O—R ¹⁶ —NR ¹¹ R ¹² is preferred.

R ¹⁵ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably. Is an alkylene group having 1 to 4 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.

R ¹⁶ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably. Is an alkylene group having 1 to 4 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.

  Specific examples of the vinyl monomer forming the structural unit represented by the general formula (1) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) ) Acrylate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide and the like.

  The content of the structural unit represented by the general formula (1) is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and 98% by mass in 100% by mass of the B block. % Or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. By setting the content of the structural unit represented by the general formula (1) within this range, it is considered that the colorant has high affinity.

  The B block may have a structural unit represented by the general formula (2). The structural unit represented by the general formula (2) in the B block may be only one type, or may have two or more types. If B block has the structural unit represented by General formula (2), the strong adsorptivity to the coloring material surface can be maintained over a long period of time, and the storage stability is further improved.

［式（２）において、Ｒ²¹、Ｒ²²およびＲ²³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ²¹、Ｒ²²およびＲ²³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｘ²は２価の連結基を示す。Ｒ²⁴は水素原子またはメチル基を示す。Ｙ^-は対イオンを示す。］

[In the formula (2), R ²¹ , R ²² and R ²³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ²¹ , R ²² and R ²³ may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²⁴ represents a hydrogen atom or a methyl group. Y ⁻ represents a counter ion. ]

Examples of the chain hydrocarbon group represented by R ^{21 to} R ²³ include a linear alkyl group and a branched alkyl group. As carbon number of the said linear alkyl group, C1-C20 is preferable, C1-C10 is more preferable, and C1-C5 is further more preferable. Examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group and the like. Is mentioned. As carbon number of the said branched alkyl group, C3-C20 is preferable, C3-C10 is more preferable, C3-C5 is further more preferable. Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, neopentyl group, and isooctyl group.

Examples of the substituent that the chain hydrocarbon group represented by R ^{21 to} R ²³ has include a halogen group, an alkoxy group, a benzoyl group (—COC ₆ H ₅ ), and a hydroxy group.

Examples of the cyclic hydrocarbon group represented by R ^{21 to} R ²³ include a cyclic alkyl group and an aromatic group, and the cyclic alkyl group and the aromatic group may have a chain portion. As carbon number of the said cyclic alkyl group, C4-C18 is preferable, C6-C12 is more preferable, C6-C10 is further more preferable. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. As carbon number of the said aromatic group, C6-C18 is preferable, C6-C12 is more preferable, and C6-C8 is further more preferable. Examples of the aromatic group include a phenyl group, a tolyl group, a xylyl group, and a mesityl group. Examples of the cyclic alkyl group having a chain portion and the chain portion of an aromatic group having a chain portion include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably carbon. Examples of the alkylene group include 1 to 3.

Examples of the substituent that the cyclic hydrocarbon group represented by R ^{21 to} R ²³ has include a halogen group, an alkoxy group, a chain alkyl group, and a hydroxy group.

Examples of the cyclic structure formed by bonding two or more of R ^{21 to} R ²³ to each other include a 5-membered to 7-membered nitrogen-containing heterocycle or a condensed ring formed by condensing two of these. It is done. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring. Specific examples include structures represented by the following formulas (2-1), (2-2), and (2-3).

［一般式（２−１）、（２−２）、（２−３）において、Ｒ²⁵は、Ｒ²¹〜Ｒ²³のいずれかである。Ｒ²⁶は、炭素数１〜６のアルキル基を示す。ｌは０〜５の整数を表す。ｍは０〜４の整数を表す。ｎは０〜４の整数を表す。＊は結合手を表す。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ²⁶は、それぞれ同一でも異なっていてもよい。］

[In General Formulas (2-1), (2-2), and (2-3), R ²⁵ is any one of R ^{21 to} R ²³ . R ²⁶ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5; m represents an integer of 0 to 4. n represents an integer of 0 to 4. * Represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ²⁶ may be the same or different. ]

In the general formula (2), examples of the divalent linking group X ² include an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH—R ²⁷ — group (amide group), a —COO—R ²⁸ — group. (ester group) and the like, preferably -CONH-R ²⁷ - a group - groups and / or -COO-R ²⁸ - a group, more preferably -COO-R ^28. The bonding direction of the amide group and the ester group is not particularly limited, but the bonding mode of the amide group is preferably C—CO—NH—R ²⁷ —N ⁺ R ²¹ R ²² R ²³ , and the bonding mode of the ester group is C—CO—O—R ²⁸ —N ⁺ R ²¹ R ²² R ²³ is preferred.

R ²⁷ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably. Is an alkylene group having 1 to 4 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.

R ²⁸ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably. Is an alkylene group having 1 to 4 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.

Examples of Y ⁻ include a halogen anion, an alkyl carboxylate anion, a nitroxide anion, an alkyl sulfate anion, a sulfonate anion, a phosphate anion, and an alkyl phosphate anion.
Examples of the halogen anion include a fluoro anion, a chloro anion, a bromo anion, and an iodo anion.
Examples of the alkyl carboxylate anion include an alkyl carboxylate anion such as an alkyl carboxylate anion such as an acetate anion and a propionate anion; and an aromatic carboxylate anion such as a benzoate anion.
Examples of the sulfate anion include alkyl sulfate anions such as methyl sulfate anion and ethyl sulfate anion; aromatic sulfate anions such as phenyl sulfate anion and benzyl sulfate anion.
Examples of the sulfonate anion include alkyl sulfonate anions such as methanesulfonate anion and ethanesulfonate anion; and aromatic sulfonate anions such as benzenesulfonate anion and toluenesulfonate anion.

  Specific examples of the vinyl monomer forming the structural unit represented by the formula (2) include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxypropyltrimethylammonium chloride, (meth) acryloyloxybutyltrimethylammonium chloride. , (Meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxypropylbenzyldimethylammonium chloride, (meth) acryloyloxybutylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride, (meth) acryloyloxy Propylbenzyldiethylammonium chloride, (meth) acryloyloxybutylbenzyldiethyl Ammonium chloride, (meth) acryloylamidopropylbenzyldimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium bromide, (meth) acryloyloxypropyltrimethylammonium bromide, (meth) acryloyloxybutyltrimethylammonium bromide, (meth) acryloyloxyethyl Benzyldimethylammonium bromide, (meth) acryloyloxypropylbenzyldimethylammonium bromide, (meth) acryloyloxybutylbenzyldimethylammonium bromide, (meth) acryloyloxyethylbenzyldiethylammonium bromide, (meth) acryloyloxypropylbenzyldiethylammonium bromide, ( Meta) Acrylo Illu Cibutylbenzyldiethylammonium bromide, (meth) acryloylamidopropylbenzyldimethylammonium bromide, (meth) acryloyloxyethyltrimethylammonium iodide, (meth) acryloyloxypropyltrimethylammonium iodide, (meth) acryloyloxybutyltrimethylammonium iodide (Meth) acryloyloxyethylbenzyldimethylammonium iodide, (meth) acryloyloxypropylbenzyldimethylammonium iodide, (meth) acryloyloxybutylbenzyldimethylammonium iodide, (meth) acryloyloxyethylbenzyldiethylammonium iodide, ( (Meth) acryloyloxypropylbenzyl diethylammonium iodide, (Meth) acryloyloxybutylbenzyldiethylammonium iodide, (meth) acryloyloxyethyltrimethylammonium fluoride, (meth) acryloyloxypropyltrimethylammonium fluoride, (meth) acryloyloxybutyltrimethylammonium fluoride, (meth) acryloyloxy Ethylbenzyldimethylammonium fluoride, (meth) acryloyloxypropylbenzyldimethylammonium fluoride, (meth) acryloyloxybutylbenzyldimethylammonium fluoride, (meth) acryloyloxyethylbenzyl diethylammonium fluoride, (meth) acryloyloxypropylbenzyl Diethylammonium fluoride, (meth) acryloyloxybutylbenzyl diethyl Numonium fluoride, (meth) acryloyloxyethyltrimethylammonium = methyl sulfate, (meth) acryloyloxypropyltrimethylammonium = methylsulfate, (meth) acryloyloxybutyltrimethylammonium = methylsulfate, (meth) acryloyloxyethyldimethyl Ethylammonium = ethylsulfate, (meth) acryloyloxypropyldimethylethylammonium = ethylsulfate, (meth) acryloyloxybutyldimethylethylammonium = ethylsulfate, (meth) acryloyloxyethyltrimethylammonium = toluene-4-sulfonate, (Meth) acryloyloxypropyltrimethylammonium = toluene-4-sulfonate, ( Data) acryloyloxybutyl trimethylammonium = toluene-4-sulfonate, (meth) acryloyl amidopropyl trimethylammonium = methyl sulfate, and (meth) acryloyl amidopropyl dimethylammonium = ethyl sulfate and the like.

  When the structural unit represented by the general formula (2) is contained, the content is preferably 2% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more in 100% by mass of the B block. 90 mass% or less is preferable, More preferably, it is 70 mass% or less, More preferably, it is 50 mass% or less. By setting the content of the structural unit represented by the general formula (2) within this range, it is considered that the colorant has high affinity.

  The B block may be only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may include other structural units. From the viewpoint of maintaining affinity with the coloring material, the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the B block is 100 masses of the B block. % Is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. Moreover, it is preferable that B block does not contain the structural unit derived from the vinyl monomer which has an acidic group substantially. That is, the content of the structural unit derived from the vinyl monomer having an acidic group is preferably 5% by mass or less, and more preferably 2% by mass or less in 100% by mass of the B block.

  Specific examples of the vinyl monomer capable of forming another structural unit of the B block include the same ones as exemplified as specific examples of the vinyl monomer capable of forming the other structural unit of the A block.

  When two or more types of structural units are contained in the B block, the various structural units contained in the B block may be contained in any form such as random copolymerization and block copolymerization in the B block. From the viewpoint of uniformity, it is preferably contained in the form of random copolymerization. For example, the B block may be formed of a copolymer of a structural unit composed of a b1 block and a structural unit composed of a b2 block.

(Block copolymer)
The structure of the block copolymer is preferably a linear block copolymer. The linear block copolymer may have any structure (arrangement). From the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the A block is A and the B block is B. when expressed as, (a-B) _m type, (a-B) _m -A type, the group consisting of (B-a) _m -B type (m is an integer of 1 or more, for example, an integer of 1 to 3) It is preferably a copolymer having at least one structure selected from Among these, it is preferable that it is an AB type | mold diblock copolymer from a viewpoint of the handleability at the time of a process, and the physical property of a composition. By constituting the AB type diblock copolymer, the structural unit derived from the (meth) acrylic monomer in the A block and the structural unit represented by the general formula (1) in the B block are localized. It is considered that the colorant, the dispersion medium (solvent), and the binder resin (alkali-soluble resin) can be effectively operated efficiently. The block copolymer may have a block other than the A block and the B block.

  The content of the A block is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and preferably 85% by mass or less, in 100% by mass of the entire block copolymer. More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less. The content of the B block is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and preferably 65% by mass or less, in 100% by mass of the entire block copolymer. More preferably, it is 60 mass% or less, More preferably, it is 55 mass% or less. By adjusting the content ratio of the A block and the B block within the above range, the dispersion performance when used as a dispersant is further improved.

  The mass ratio of the A block to the B block in the block copolymer (A block / B block) is preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, and 95 / 5 or less is preferable, more preferably 90/10 or less, and still more preferably 80/20 or less. When the mass ratio of the A block and the B block is within the above range, the dispersion performance when used as a dispersant is further improved.

  When the block copolymer contains a structural unit having an acidic group, the content of the structural unit derived from the vinyl monomer having an acidic group in the block copolymer is preferably 1% by mass or more, more preferably 2%. % By mass or more, more preferably 3% by mass or more, preferably 10% by mass or less, more preferably 9% by mass or less, and still more preferably 8% by mass or less.

  The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the block copolymer is preferably 5% by mass or more, more preferably 10% by mass. As mentioned above, More preferably, it is 20 mass% or more, 50 mass% or less is preferable, More preferably, it is 45 mass% or less, More preferably, it is 40 mass% or less.

  The molecular weight of the block copolymer is measured by a gel permeation chromatography (hereinafter referred to as “GPC”) method. The weight average molecular weight (Mw) of the block copolymer is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, particularly preferably 6,000 or more, Is preferably 30,000 or less, more preferably 30,000 or less, still more preferably 25,000 or less, and particularly preferably 20,000 or less. When the weight average molecular weight is within the above range, the dispersion performance when used as a dispersant becomes better.

  The molecular weight distribution (PDI) of the block copolymer is preferably 2.5 or less, more preferably 2.0 or less, and still more preferably 1.6 or less. In the present invention, the molecular weight distribution (PDI) is determined by (weight average molecular weight (Mw) of block copolymer) / (number average molecular weight (Mn) of block copolymer). The smaller the PDI, the narrower the molecular weight distribution and the more uniform the copolymer. When the value is 1.0, the molecular weight distribution is the narrowest. That is, the lower limit value of PDI is 1.0. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.5, one having a low molecular weight or one having a high molecular weight is included.

  The amine value of the block copolymer is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 30 mgKOH / g or more, from the viewpoints of adsorbability to the colorant and dispersibility of the colorant. 200 mgKOH / g or less is preferable, More preferably, it is 150 mgKOH / g or less, More preferably, it is 100 mgKOH / g or less.

  When the block copolymer contains a structural unit having an acidic group, the acid value of the block copolymer is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 15 mgKOH / g or more. 50 mgKOH / g or less, more preferably 40 mgKOH / g or less, and still more preferably 35 mgKOH / g or less. By setting the acid value within this range, the binder resin (alkali-soluble resin) can be suitably acted on without impairing the affinity of the block copolymer with the colorant.

(Method for producing block copolymer)
The block copolymer is produced by a method in which an A block is first produced by a polymerization reaction of a vinyl monomer, and a B block monomer is polymerized in the A block; A method of polymerizing monomers of the block; a method of coupling the A block and the B block after separately producing the A block and the B block, and the like.

  The polymerization method is not particularly limited, but living radical polymerization is preferred. In other words, the block copolymer is preferably polymerized by living radical polymerization. In the conventional radical polymerization method, not only the initiation reaction and the growth reaction, but also the termination of the growth end occurs due to the termination reaction and the chain transfer reaction, and the polymer tends to be a mixture of polymers having various molecular weights and heterogeneous compositions. In contrast, the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method, but it is difficult to cause a termination reaction or chain transfer, and the growth end grows without being deactivated. Precise control is preferable in that the production of a polymer having a uniform composition is easy.

  In the living radical polymerization method, a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); There are methods such as a method to be used (TERP method). Since the ATRP method uses an amine-based complex, it may not be used without protecting the acidic group of the vinyl monomer having an acidic group. In the RAFT method, when various monomers are used, it is difficult to obtain a low molecular weight distribution, and there may be a problem such as sulfur odor or coloring. Among these methods, the TERP method is preferably used from the viewpoint of diversity of usable monomers, molecular weight control in the polymer region, uniform composition, or coloring.

  The TERP method is a method of polymerizing a radical polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent. For example, International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and WO 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d).
(A) A vinyl monomer is polymerized using an organic tellurium compound represented by the general formula (3).
(B) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator.
(C) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (3) and an organic ditelluride compound represented by the general formula (4).
(D) The vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (3), an azo polymerization initiator, and an organic ditelluride compound represented by the general formula (4).

［一般式（３）において、Ｒ³¹は、炭素数１〜８のアルキル基、アリール基または芳香族ヘテロ環基を示す。Ｒ³²およびＲ³³は、それぞれ独立に、水素原子または炭素数１〜８のアルキル基を示す。Ｒ³⁴は、炭素数１〜８のアルキル基、アリール基、置換アリール基、芳香族ヘテロ環基、アルコキシ基、アシル基、アミド基、オキシカルボニル基、シアノ基、アリル基またはプロパルギル基を示す。
一般式（４）において、Ｒ³¹は、炭素数１〜８のアルキル基、アリール基または芳香族ヘテロ環基を示す。］

[In General Formula (3), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group. R ³² and R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ³⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.
In the general formula (4), R ³¹ represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms. ]

The group represented by R ³¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group, and is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. And a linear or branched alkyl group such as a octyl group and a cyclic alkyl group such as a cyclohexyl group. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.

The groups represented by R ³² and R ³³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. And a linear or branched alkyl group such as a octyl group and a cyclic alkyl group such as a cyclohexyl group. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.

The group represented by R ³⁴ is an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or A propargyl group, specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. And a linear or branched alkyl group such as an octyl group, a cyclic alkyl group such as a cyclohexyl group, and the like. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group. A phenyl group is preferred.
Examples of the substituted aryl group include a phenyl group having a substituent and a naphthyl group having a substituent. Examples of the substituent of the aryl group having the substituent include a halogen atom, a hydroxy group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by —COR ³⁴¹ (R ³⁴¹ is carbon (C1-C8 alkyl group, aryl group, C1-C8 alkoxy group or aryloxy group), sulfonyl group, trifluoromethyl group and the like. These substituents are preferably substituted by 1 or 2 substituents.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
As the alkoxy group, a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom is preferable. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert- Examples include butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.
Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
Examples of the amide group include —CONR ³⁴²¹ R ³⁴²² (R ³⁴²¹ and R ³⁴²² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group).
As the oxycarbonyl group, a group represented by —COOR ³⁴³¹ (R ³⁴³¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group) is preferable, and examples thereof include a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group. Group, n-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, phenoxycarbonyl group and the like. Preferred oxycarbonyl groups include methoxycarbonyl group and ethoxycarbonyl group.
As an allyl group, —CR ³⁴⁴¹ R ³⁴⁴² —CR ³⁴⁴³ = CR ³⁴⁴⁴ R ³⁴⁴⁵ (R ³⁴⁴¹ and R ³⁴⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³⁴⁴³ , R ³⁴⁴⁴ and R ³⁴⁴⁵ are And each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and each substituent may be linked by a cyclic structure).
As the propargyl group, —CR ³⁴⁵¹ R ³⁴⁵² —C≡CR ³⁴⁵³ (R ³⁴⁵¹ and R ³⁴⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³⁴⁵³ is a hydrogen atom and an alkyl group having 1 to 8 carbon atoms) , Aryl group or silyl group).

  Specific examples of the organic tellurium compound represented by the general formula (3) include (methylterranylmethyl) benzene, (methylterranylmethyl) naphthalene, ethyl-2-methyl-2-methylterranyl-propionate, ethyl-2- Methyl-2-n-butylterranyl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methylterranyl-propionate, (2-hydroxyethyl) -2-methyl-2-methylterranyl-propionate or (3-trimethylsilylpropargyl ) -2-methyl-2-methylterranyl-propionate, etc., organics described in International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and International Publication No. 2004/096870 All of the tellurium compounds It can Shimesuru.

  Specific examples of the organic ditelluride compound represented by the general formula (4) include dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, dicyclopropylditelluride, -N-butyl ditelluride, di-s-butyl ditelluride, di-t-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis Examples include-(p-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride or dipyridyl ditelluride.

  The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization. For example, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), 2,2′-azobis (2,4-dimethylvaleronitrile) ) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid ) (ACVA), 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methylbutyramide), 2,2′-azobis (4-methoxy-2,4) -Dimethylvaleronitrile) (V-70), 2,2'-azobis (2-methylamidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) Lopan], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2-cyano-2-propyl Examples include azoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), and the like.

  The polymerization process is a container substituted with an inert gas. For the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution according to the type of vinyl monomer, the organic tellurium compound of the general formula (3), and the vinyl monomer, azo A system polymerization initiator and / or an organic ditelluride compound of the general formula (4) are mixed. At this time, examples of the inert gas include nitrogen, argon, helium and the like. Argon and nitrogen are preferable.

  What is necessary is just to adjust suitably the usage-amount of the vinyl monomer in said (a), (b), (c) and (d) according to the physical property of the target copolymer. The vinyl monomer is preferably 5 mol to 10000 mol with respect to 1 mol of the organic tellurium compound of the general formula (3).

  When the organic tellurium compound of the general formula (3) and the azo polymerization initiator of (b) are used in combination, the azo polymerization initiator is used in an amount of 0.01 mol to 10 mol with respect to 1 mol of the organic tellurium compound of the general formula (3). It is preferable that

  When the organic tellurium compound of the general formula (3) of the above (c) and the organic ditelluride compound of the general formula (4) are used in combination, the organic of the general formula (4) is used per 1 mol of the organic tellurium compound of the general formula (3). The ditelluride compound is preferably 0.01 mol to 100 mol.

  When the organic tellurium compound of the general formula (3) of (d), the organic ditelluride compound of the general formula (4), and the azo polymerization initiator are used in combination, it is generally used with respect to 1 mol of the organic tellurium compound of the general formula (3). The organic ditelluride compound of the formula (4) is preferably 0.01 mol to 100 mol, and the azo polymerization initiator is preferably 0.01 mol to 10 mol with respect to 1 mol of the organic tellurium compound of the general formula (3).

  The polymerization reaction can be carried out without a solvent, but it may be carried out using an aprotic solvent or a protic solvent generally used in radical polymerization and stirring the mixture. Examples of aprotic solvents that can be used include anisole, benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform. , Carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, trifluoromethylbenzene, and the like. Examples of the protic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, and diacetone alcohol.

  The amount of the solvent used may be adjusted as appropriate. For example, it is preferably 0.01 ml or more, more preferably 0.05 ml or more, still more preferably 0.1 ml or more, and 50 ml or less with respect to 1 g of vinyl monomer. More preferably, it is 10 ml or less, More preferably, it is 1 ml or less.

  The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the copolymer to be obtained, but are usually stirred at 0 ° C. to 150 ° C. for 1 minute to 100 hours. The TERP method can obtain a high yield and a precise molecular weight distribution even at a low polymerization temperature and a short polymerization time. At this time, the pressure is usually normal pressure, but it may be increased or decreased.

  After the completion of the polymerization reaction, the intended copolymer can be separated from the obtained reaction mixture by removing the solvent used, residual vinyl monomer, and the like by a normal separation and purification means.

The growth terminal of the copolymer obtained by the polymerization reaction is in the form of -TeR ³¹ derived from a tellurium compound (wherein R ³¹ is the same as above), and is deactivated by the operation in the air after the completion of the polymerization reaction. However, tellurium atoms may remain. Since the copolymer in which the tellurium atom remains at the terminal is colored or inferior in thermal stability, it is preferable to remove the tellurium atom.

  As a method for removing tellurium atoms, a radical reduction method using tributylstannane or a thiol compound; a method of adsorbing with activated carbon, silica gel, activated alumina, activated clay, molecular sieves, polymer adsorbent, etc .; Method of adsorbing metal: Add peroxide such as hydrogen peroxide or benzoyl peroxide, or blow air or oxygen into the system to oxidatively decompose tellurium atoms at the end of the copolymer. Liquid-liquid extraction methods and solid-liquid extraction methods that remove residual tellurium compounds by combining solvents; purification methods such as ultrafiltration that extracts and removes only those having a specific molecular weight or less can be used. These methods can also be used in combination.

  When the tertiary amine group of the structural unit represented by the formula (1) is quaternized, examples of the quaternizing agent include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide; benzyl chloride Aralkyl halides such as benzyl bromide and benzyl iodide; diaryl sulfates such as diphenyl sulfate; dialkyl sulfates such as dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate; methyl p-toluenesulfonate; p-toluenesulfonic acid Examples thereof include an alkyl alkyl sulfonate such as ethyl. Among these, preferably aralkyl halides such as benzyl chloride, benzyl bromide and benzyl iodide, dialkyl sulfates such as dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate, methyl p-toluenesulfonate, p-toluenesulfone Aromatic alkyl sulfonates such as ethyl acid, and more preferably benzyl chloride, dimethyl sulfate, and methyl p-toluenesulfonate. In the structure after quaternization, an alkyl group and an aralkyl group derived from a quaternizing agent are introduced. Therefore, the amount of the structural unit represented by the formula (2) can be estimated by measuring the amount of the alkyl group and aralkyl group introduced by quaternization.

  Examples of the method for quaternizing a tertiary amine structure of a part of the structural unit represented by the formula (1) in the polymer include a method of bringing the polymer into contact with a quaternizing agent. Specifically, after polymerizing a monomer composition containing a vinyl monomer capable of forming the structural unit represented by the formula (1), a quaternizing agent is added to the reaction solution and stirred. . The temperature of the reaction solution to which the quaternizing agent is added is preferably 25 ° C to 65 ° C, more preferably 55 ° C to 65 ° C, and the stirring time is preferably 1 hour to 40 hours, more preferably 5 hours to 20 hours. It is. When adding the quaternizing agent, it is also preferable to dilute the reaction solution after polymerization. Examples of the solvent added for dilution include a solvent that can be used for the polymerization reaction, a protic solvent, and a mixed solvent of the solvent used for the polymerization reaction and the protic solvent, depending on the solubility of the target block copolymer. What is necessary is just to select suitably. As the protic solvent, methanol is more preferable.

(Phosphorous ester)
The dispersant composition of the present invention contains a phosphite represented by the general formula (5). By containing a phosphite, formaldehyde generated from the resin-type dispersant can be reduced. Moreover, when the resin-type dispersant is exposed to a high temperature, oxidation of amino groups can be suppressed and yellowing of the dispersant composition can be suppressed. The phosphorous acid ester represented by General formula (5) may be used individually by 1 type, and may use 2 or more types together.

［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. R ⁵² and R ⁵³ each independently represents a hydrocarbon group. R ⁵² and R ⁵³ may be bonded to each other to form a cyclic structure. The compound represented by the general formula (5) may be bonded with 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 the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, 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 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. 1-20 are preferable, as for the carbon number of the whole alkyl group which may have the said substituent, More preferably, it is 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 Examples include chain alkyl groups such as octadecyl group and eicosyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, methylcyclopentyl group, and methylcyclohexyl group. Examples of the aromatic group include phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group, benzyl group, phenethyl group, styryl group, cinnamyl group, benzhydryl group, trityl group, ethylphenyl group, propylphenyl group, butylphenyl group. 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 be bonded to each other to form a cyclic structure. Examples of the ring formed by combining R ⁵² and R ⁵³ with each other include the following partial structures. Furthermore, the compound represented by the general formula (5) may be bonded with R ⁵² or R ⁵³ to form a dimer or trimer.

  As a phosphite represented by the general formula (5), a phosphite ester represented by the general formula (5-1) and / or a phosphite ester 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. A plurality of 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. A plurality of R ⁵¹ may be the same or different. ]

  Examples of the phosphite 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; octyl diphenyl phosphite, decyl diphenyl phosphite, diphenyl phosphite Alkyl diphenyl phosphites such as isodecyl, tridecyl diphenyl phosphite, hexadecyl diphenyl phosphite; 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] dimer, etc. phosphites of undecane. Among these, trialkyl phosphite is preferable, and tributyl phosphite and triisodecyl phosphite are more preferable.

  The phosphorous acid ester represented by the general formula (5) contained in the dispersant composition may be only one type or a plurality of types. In the dispersant composition, the content of the phosphite represented by the general formula (5) is preferably 0.1 parts by mass or more, more preferably 0.5 parts per 100 parts by mass of the resin-type dispersant. It is at least 1.0 part by mass, more preferably at least 15 parts by mass, more preferably at most 10 parts by mass, even more preferably at most 8 parts by mass, particularly preferably at most 5 parts by mass.

  In the dispersant composition, the molar ratio of the tertiary amino group of the resin-type dispersant to the phosphite represented by the general formula (5) (phosphite / amino group) is 0.001. The above is preferable, more preferably 0.005 or more, still more preferably 0.01 or more, and 0.5 or less is preferable, more preferably 0.3 or less, and still more preferably 0.2 or less. When the molar ratio is within the above range, the effect of reducing formaldehyde and the effect of suppressing yellowing of the dispersant composition are further improved. On the other hand, when the molar ratio exceeds 0.5, the viscosity of the dispersant composition and the coloring composition tends to increase. The amino group that the block copolymer has can be calculated from the amine value.

(Phenolic antioxidant)
The dispersant composition may contain a known phenolic antioxidant. By containing a phenolic antioxidant, the amount of formaldehyde in the dispersant composition can be further reduced. The reason why the amount of formaldehyde can be reduced is considered to be because the oxidative deterioration of the phosphite can be suppressed.

  The phenol-based 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 in 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 Such as 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

  As said phenolic antioxidant, the compound represented by General formula (6) is preferable.

［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 the general formula (6), R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ^R62 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 a hydrocarbon group having 2 to 20 carbon atoms are substituted with an ester group or an ether group, or a hydrocarbon group having 1 to 20 carbon atoms. n represents the number of 1-6. 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 methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, 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 because the synergistic effect of antioxidant performance is great. In R ^61, the carbon atom bonded to the benzene ring does not become a quaternary carbon atom. For example, a group such as a tert-butyl group is ineligible as R ⁶¹ .

^R62 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 a hydrocarbon group having 2 to 20 carbon atoms are 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 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, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, isoundecyl, dodecyl, isododecyl, tridecyl, isotridecyl, tetradecyl, isotetradecyl, hexadecyl, isohexadecyl Group, octadecyl group, isooctadecyl group, eicosyl group and the like alkyl group; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, isopentenyl group, hexenyl group, heptenyl group, octenyl group , Nonenyl , Decenyl group, undecenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and other alkenyl groups; phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group, benzyl group, phenethyl group, styryl group, 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, dodecylphenyl group Aryl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, methylcyclopentyl group, methylcyclohexyl group and the like. 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, A value of 3 is a group obtained by removing two arbitrary hydrogen atoms from the above group. Although the value of n represents the number of 1-6, the number of 1-4 is preferable and the number of 2 or 3 is more preferable because the performance as an antioxidant is favorable and the raw material situation is favorable.

R ⁶³ may be a group in which one or more carbon atoms of a hydrocarbon group 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, may have both, or may have a plurality. From the viewpoint of a synergistic effect with the phosphite, 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, 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 dispersant composition may be only one type or a plurality of types. In the dispersant 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, further preferably 1 with respect to 100 parts by mass of the resin-type dispersant. 0.0 part by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less.

  The mass ratio of the phosphite ester represented by the general formula (5) and the phenolic antioxidant contained in the dispersant composition (phenolic antioxidant / phosphite ester) is 0.01 or more. More preferably, it is 0.05 or more, More preferably, it is 0.1 or more, 1 or less is preferable, More preferably, it is 0.7 or less, More preferably, it is 0.5 or less. When the mass ratio is within the above range, the amount of formaldehyde in the dispersant composition can be further reduced by a synergistic effect with the phosphite represented by the general formula (5). On the other hand, when the mass ratio exceeds 1, the viscosity of the dispersant composition and the coloring composition tends to increase.

(Dispersion medium)
The dispersant composition may contain a dispersion medium. The dispersion medium can be appropriately selected and used as long as it disperses or dissolves the resin-type dispersant and the phosphite ester and does not react with these components and has moderate volatility. For example, conventionally known organic solvents can be used, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl 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, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene Glycol monomethyl ether, 3-methyl Glycol monoalkyl ethers such as 3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Glycol dialkyl ethers such as 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 monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono- Glycol alkyl ether acetates such as n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate; ethylene glycol Glycol diacetates such as rudiacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether Ethers such as butyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, Ketones such as methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone; Monovalent or polyhydric alcohols such as butanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, methoxymethylpentanol, glycerin, benzyl alcohol Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, vinegar Amyl, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, 3 -Chain or cyclic esters such as ethyl ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate and γ-butyrolactone; 3-methoxypropion Acids, alkoxycarboxylic acids such as 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; acetonitrile, benzonitrile And the like nitriles such as is.

  The content of the dispersion medium in the dispersant composition is not particularly limited and can be adjusted as appropriate. The upper limit of the content of the dispersion medium in the dispersant composition is usually 99% by mass. Further, the lower limit of the content of the dispersion medium in the dispersant composition is usually 30% by mass and preferably 45% by mass in consideration of the viscosity suitable for the production of the colored composition described later.

<Coloring composition>
The coloring composition of this invention contains the said dispersing agent composition, a coloring material, binder resin, and a dispersion medium.

(Coloring material)
What is necessary is just to select the kind of said coloring material suitably according to the use, for example, a pigment and dye are mentioned. The colored composition preferably contains a pigment as a coloring material from the viewpoint of light resistance and heat resistance. The pigment may be either an organic pigment or an inorganic pigment, but an organic pigment mainly composed of an organic compound is particularly preferable. Examples of the pigment include pigments of various colors such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, and a purple pigment. The structure of the pigment is azo pigments such as monoazo pigments, diazo pigments, condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo Examples thereof include polycyclic pigments such as pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments. Only one type of pigment may be included in the coloring composition, or a plurality of types may be used for adjusting chromaticity and the like.

  Specific examples of the pigment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, 146, 149, 166, 168, Red pigments such as 177, 178, 179, 187, 200, 202, 208, 210, 215, 224, 242, 254, 255, 264, 269; I. Pigment Yellow 1, 3, 5, 6, 14, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 93, 97, 98, 104, 108, 110, 138, 139, 147, Yellow pigments such as 150, 151, 154, 155, 166, 167, 168, 170, 180, 185, 188, 193, 194, 213; I. Orange pigments such as CI Pigment Orange 36, 38, 43; I. Pigment Blue 15, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60 and the like; C.I. I. Pigment Green 7, 36, 58, 59, 62, 63, aluminum phthalocyanine, polyhalogenated aluminum phthalocyanine, aluminum phthalocyanine hydroxide, diphenoxyphosphinyloxyaluminum phthalocyanine, diphenylphosphinyloxyaluminum phthalocyanine, polyhalogenated diphenoxy Green pigments such as phosphinyloxyaluminum phthalocyanine and polyhalogenated diphenylphosphinyloxyaluminum phthalocyanine; I. And a violet pigment such as Pigment Violet 23, 29, 32, and 50. Among these pigments, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 269, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59 and the like are preferable.

  The number average particle diameter of the colorant may be appropriately selected according to the application and is not particularly limited. The colored composition preferably contains a colorant having a number average particle size of 10 nm to 150 nm from the viewpoint of high transparency and high contrast.

  The colorant may contain a pigment derivative as a dispersion aid. The dye derivative preferably contains an acidic dye derivative having an acidic group so as to be ion-bonded and adsorbed with a tertiary amino group or a quaternary ammonium base in the resin-type dispersant. This dye derivative has an acidic functional group introduced into the dye skeleton. As the dye skeleton, a skeleton that is the same as or similar to the colorant constituting the coloring composition and a skeleton that is the same as or similar to the compound that is the raw material of the pigment are preferable. Specific examples of the dye skeleton include azo dye skeleton, phthalocyanine dye skeleton, anthraquinone dye skeleton, triazine dye skeleton, acridine dye skeleton, and perylene dye skeleton. The acidic group introduced into the dye skeleton is preferably a carboxy group, a phosphoric acid group, or a sulfonic acid group. In addition, a sulfonic acid group is preferable from the viewpoint of synthesis and the strength of acidity. The acidic group may be directly bonded to the dye skeleton, but 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. Although the usage-amount of a pigment derivative does not have limitation in particular, For example, it is preferable that they are 4 mass parts-17 mass parts with respect to 100 mass parts of coloring materials.

  The upper limit of the content of the coloring material in the coloring composition is usually 80% by mass, preferably 70% by mass, and preferably 60% by mass in the total solid content of the coloring composition from the viewpoint of luminance. It is more preferable. Further, the lower limit of the content of the coloring material in the coloring composition is usually 10% by mass, preferably 20% by mass, more preferably 30% by mass in the total solid content of the coloring composition. preferable. Here, solid content is components other than the dispersion medium mentioned later.

  The content of the resin-type dispersant with respect to the colorant in the coloring composition is preferably 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the colorant, and preferably 10 parts by mass to 100 parts by mass. More preferably, it is 10 mass parts-80 mass parts.

(Binder resin)
The colored composition contains a binder resin (excluding the resin-type dispersant). Thereby, the alkali developability of a coloring composition and the binding property to a board | substrate can be improved. Such a binder resin is not particularly limited, but is preferably a resin having an acidic group such as a carboxy group or a phenolic hydroxy group. As the binder resin, for example, with respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, at least a part of the epoxy group of the copolymer is unsaturated monobasic. Resin obtained by adding an acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxy group generated by the addition reaction; a linear alkali-soluble resin containing a carboxy group in the main chain Resin; Resin in which an epoxy group-containing unsaturated compound is added to the carboxy group portion of a carboxy group-containing resin; (meth) acrylic resin; epoxy (meth) acrylate resin having a carboxy group, and the like. These can be used alone or in admixture of two or more.

  Examples of the binder resin include a random copolymer containing a structural unit derived from a carboxy group-containing vinyl monomer, a structural unit derived from (meth) acrylate, and styrene, a structural unit derived from a carboxy group-containing vinyl monomer, ) Random copolymers containing structural units derived from acrylates are preferred. As the carboxy group-containing vinyl monomer, (meth) acrylic acid is preferable. Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and cyclohexyl (meth) acrylate. , Isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxylethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono ( And (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like. That.

  In the binder resin, the total content of the structural unit derived from the carboxy group-containing vinyl monomer and the structural unit derived from (meth) acrylate is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably. 70% by mass or more. The binder resin preferably has a structure content derived from a carboxy group-containing vinyl monomer of 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 90% by mass or less. Is more preferable, and 70% by mass or less is more preferable.

  Among these, a random copolymer of a carboxy group-containing vinyl monomer and (meth) acrylate is preferable. Specific examples of such a copolymer include a random copolymer of (meth) acrylic acid and butyl (meth) acrylate, a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate, (meth ) Random copolymers of acrylic acid, butyl (meth) acrylate and benzyl (meth) acrylate. From the viewpoint of the affinity between the binder resin and the colorant, the binder resin is particularly preferably a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate.

  In the copolymer of a carboxy group-containing vinyl monomer and (meth) acrylate, the content of (meth) acrylic acid is usually 5% by mass to 90% by mass, and 10% by mass to 70% by mass in all monomer components. It is preferable that it is 20 mass%-70 mass%.

  The binder 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 colored composition according to the present invention is increased, 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 vinyl benzyl glycidyl ether with the acidic group of the binder resin.

  The Mw of the binder resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 20,000. When the Mw of the binder resin is 3,000 or more, the heat resistance, film strength and the like of the colored layer formed from the colored composition are improved, and when the Mw is 100,000 or less, the alkali developability of this coating film Is even better.

  The acid value of the binder resin is preferably 20 mgKOH / g to 170 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and still more preferably 90 mgKOH / g to 150 mgKOH / g. When the acid value of the binder resin is 20 mgKOH / g or more, the alkali developability when the colored composition is used as a colored layer is further improved, and when it is 170 mgKOH / g or less, the heat resistance is improved.

  The binder resin contained in the coloring composition may be only one type or a plurality of types. In the coloring composition, the content of the binder resin is preferably 3 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the colorant, and 20 parts by mass. More preferably, it is 80 parts by mass.

(Crosslinking agent)
The colored composition may contain a crosslinking agent as necessary. A cross-linking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. As the crosslinking agent, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable. The said crosslinking agent can be used individually or in mixture of 2 or more types.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional compound modified with caprolactone ( (Meth) acrylate, polyfunctional (meth) acrylate modified with alkylene oxide, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate having hydroxy group and polyfunctional isocyanate, (meth) acrylate having hydroxy group And a polyfunctional (meth) acrylate having a carboxy group obtained by reacting an acid anhydride with the acid anhydride.

  Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; trivalent or more such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Of the aliphatic polyhydroxy compound. Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and di Examples include pentaerythritol hexa (meth) acrylate and glycerol dimethacrylate. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride; pyromellitic anhydride, biphenyltetracarboxylic acid And tetrabasic acid dianhydrides such as acid dianhydride and benzophenone tetracarboxylic dianhydride.

  In the coloring composition, the content of the crosslinking agent is preferably 10 parts by mass to 1,000 parts by mass, and particularly preferably 20 parts by mass to 500 parts by mass with respect to 100 parts by mass of the colorant. If the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the amount of the crosslinking agent is too large, the alkali developability of the colored composition of the present invention is lowered, and background stains, film residues, etc. tend to occur on the unexposed portion of the substrate or on the light shielding layer. .

(Photopolymerization initiator)
The said coloring composition may contain a photoinitiator as needed. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator is a compound that generates active species capable of initiating polymerization of a crosslinking agent upon exposure to radiation such as visible light, ultraviolet light, far infrared light, electron beam, and X-ray.

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

  In the colored composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 parts by mass to 120 parts by mass, particularly preferably 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, the curing may be insufficient due to exposure. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

(Dispersion medium)
The coloring composition contains a dispersion medium. The dispersion medium can be appropriately selected and used as long as it disperses or dissolves other components constituting the coloring composition and does not react with these components and has an appropriate volatility. For example, a conventionally well-known organic solvent can be used, For example, the organic solvent which can be used for the said dispersing agent composition is mentioned. The organic solvent is preferably glycol alkyl ether acetates, monovalent or polyhydric alcohols from the viewpoints of dispersibility of pigments, solubility of the dispersant, applicability of the pigment dispersion composition, and the like. The solvent contained in the pigment dispersion composition may be only one type or a plurality of types.

  When forming a pixel of a color filter by a photolithography method, the boiling point of the dispersion medium is preferably 100 ° C. to 200 ° C. (under a pressure of 101.25 hPa. The same applies to the boiling points hereinafter), and 120 ° C. to 170 ° C. is preferable. More preferred. Among the above-mentioned dispersion media, glycol alkyl ether acetates are preferable from the viewpoints of good balance of coatability, surface tension, and the like, and relatively high solubility of the constituent components in the colored composition. Glycol alkyl ether acetates may be used alone or in combination with other dispersion media. In this case, it is also preferable to use a dispersion medium having a boiling point of 150 ° C. or higher. By using such a dispersion medium having a high boiling point, the colored composition becomes difficult to dry, and the destruction of the mutual relationship of the colored composition due to rapid drying can be suppressed. The content of the dispersion medium having a boiling point of 150 ° C. or higher is preferably 3% by mass to 50% by mass with respect to 100% by mass of the entire dispersion medium. When the content ratio is 3% by mass or more, it is possible to suppress the occurrence of foreign matter defects due to precipitation and solidification of the coloring material at the tip of the slit nozzle. If it is 50 mass% or less, the drying rate of a coloring composition will become slow, and generation | occurrence | production of problems, such as prolonged drying time and the pin mark of a prebaking in color filter manufacture mentioned later can be suppressed. The dispersion medium having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates. In this case, a dispersion medium having a boiling point of 150 ° C. or higher may not be included separately.

  When forming a pixel of a color filter by the inkjet method, the boiling point of the dispersion medium is preferably 130 ° C to 300 ° C, and more preferably 150 ° C to 280 ° C. By setting the boiling point to 130 ° C. or higher, the uniformity of the obtained coating film is improved. Moreover, the residual solvent in the coating film after heat baking can be reduced by making a boiling point into 300 degrees C or less, and the malfunction on quality and the prolongation of drying time can be suppressed. Further, the vapor pressure of the dispersion medium is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.

  In the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, from several pL to several tens of pL, so the dispersion medium evaporates before landing on the periphery of the nozzle opening or in the pixel bank. Tends to concentrate and dry. In order to avoid this, it is preferable that the boiling point of the dispersion medium is high. Specifically, it is preferable to include a dispersion medium having a boiling point of 180 ° C. or higher. More preferably, it contains a dispersion medium having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. Further, the high boiling point solvent having a boiling point of 180 ° C. or more is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass with respect to 100% by mass of the entire dispersion medium contained in the coloring composition. The above is most preferable. There exists a tendency which can fully exhibit the evaporation prevention effect of the solvent from a droplet by setting it as the said lower limit or more.

  Content of the dispersion medium in a coloring composition is not specifically limited, It can adjust suitably. The upper limit of the content of the dispersion medium in the coloring composition is usually 99% by mass. In addition, the lower limit of the content of the dispersion medium in the coloring composition is usually 70% by mass and preferably 80% by mass in consideration of the viscosity suitable for application of the coloring composition. The said dispersion medium can be used as a solvent for melt | dissolving and removing the precipitate formed from a coloring composition.

(Other ingredients)
If it is a range which does not impair the preferable physical property of this invention, another compounding agent other than the said compounding agent can be mix | blended with the said coloring composition. Other compounding agents include sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, plasticizers, organic carboxylic acid compounds, organic carboxylic acids Acid anhydrides, pH adjusters, antioxidants other than the above-mentioned phenolic antioxidants, UV absorbers, light stabilizers, antiseptics, fungicides, anti-aggregation agents, adhesion improvers, development improvers, storage stability An agent etc. can be mentioned.

  As the sensitizing dye, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3 , 4-Diaminobenzophenone, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- ( p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p -Diethylaminophenyl) benzothiazo 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) Examples include pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, and the like.

  Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like.

Nonionic surfactants include fluorosurfactants (1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetra Fluorooctyl hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol Di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1, 2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc.) Surfactants, polyoxyethylene surfactants (polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene Fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbite fatty acid esters And polyoxyethylene sorbite fatty acid esters).
Anionic surfactants include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, higher alcohol sulfate esters, aliphatic Alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymer surface activity Agents and the like.
Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, alkylamine salts and the like.
Examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines and amino acids.

  Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like.

  Organic carboxylic acid compounds include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid and other monocarboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid , Adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, tricarballylic acid, aconitic acid, benzoic acid, phthalic acid, etc. Examples thereof include carboxylic acids and carboxylic acids in which a carboxyl group is bonded to a phenyl group via a carbon bond.

  Examples of organic carboxylic acid anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2- Examples include cyclohexene dicarboxylic acid, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.

<Method for producing colored composition>
The colored composition can be prepared by mixing a colorant, a dispersant composition, a binder resin, a dispersion medium, and, if necessary, a crosslinking agent, a photopolymerization initiator, and other compounding agents. For the mixing, for example, a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, or a kneader can be used. The coloring composition is preferably filtered after mixing. Since the coloring composition has alkali developability, it can be suitably used for a color filter.

<Color filter>
The color filter of this invention is provided with the colored layer formed using the said coloring composition.

  Examples of the method for producing the color filter include the following methods. First, sheet made of thermoplastic resin such as polyester resin, polyolefin resin, polycarbonate resin, polymethyl methacrylate resin, thermosetting resin sheet such as epoxy resin, unsaturated polyester resin, poly (meth) acrylic resin, various glasses For example, after applying the coloring composition of the present invention in which a red pigment is dispersed on a transparent substrate such as the above, pre-baking is performed to evaporate the solvent (dispersion medium) to form a coating film. Next, the coating film is exposed through a photomask, and then developed using an alkaline developer (an organic solvent or an aqueous solution containing a surfactant and an alkaline compound) to dissolve and remove unexposed portions of the coating film. To do. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement. Next, using each colored composition of green or blue, and applying each of the colored compositions, pre-baking, exposing, developing and post-baking in the same manner as described above, the green pixel array and the blue pixel array are formed on the same substrate. Sequentially formed on top. Thereby, a color filter in which a pixel array of the three primary colors of red, green and blue is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

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

  A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film (ITO or the like) is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter.

  The color filter of the present invention has high dimensional accuracy and can be suitably used for a color liquid crystal display element, a color imaging tube element, a color sensor, an organic EL display element, electronic paper, and the like.

  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 implemented with appropriate modifications without departing from the scope of the invention. The polymerization rate of block copolymer and binder resin, weight average molecular weight (Mw), molecular weight distribution (PDI), amine value and acid value, and dispersibility, luminance and formaldehyde amount of the colored composition are as follows. Evaluated according to.

The abbreviations have the following meanings.
PCL5: 5-mol caprolactone adduct of 2-hydroxyethyl methacrylate (Daicel Chemical Industries, Plaxel (registered trademark) FM5)
BMA: butyl methacrylate DMAEMA: dimethylaminoethyl methacrylate MAA: methacrylic acid BzMA: benzyl methacrylate BTEE: ethyl-2-methyl-2-n-butyl terranyl-propionate DBDT: dibutyl ditelluride AIBN: 2,2′-azobis (isobutyrate) Ronitrile)
PMA: Propylene glycol monomethyl ether acetate AcOBu: Butyl acetate

(Polymerization rate)
¹ H-NMR was measured (solvent: CDCl ₃ , internal standard: trimethylsilane (TMS)) using a nuclear magnetic resonance (NMR) measuring apparatus (Bruker BioSpin, model: AVANCE500 (frequency 500 MHz)). . About the obtained NMR spectrum, the integration ratio of the peak of the vinyl group derived from the monomer and the peak of the ester side chain derived from the polymer was determined, and the polymerization rate of the monomer was calculated.

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))
It calculated | required from the gel permeation chromatography (GPC) using the high performance liquid chromatograph (The Tosoh make, model HLC-8320). As for the column, one SHODEX KF-603 (φ6 mm × 150 mm) (manufactured by SHODEX), 10 mmol / L lithium bromide / 10 mmol / L acetic acid / N-methyl-2-pyrrolidone solution as a mobile phase, and differential refractometer as a detector It was used. The measurement conditions were a column temperature of 40 ° C., a sample concentration of 10 mg / mL, a sample injection amount of 10 μm, and a flow rate of 0.2 mL / min. A calibration curve (calibration curve) was prepared using polystyrene (molecular weight 427,000, 190,000, 96,400, 37,400, 10,200, 2,630, 906) as a standard substance, and the weight average molecular weight ( Mw) and number average molecular weight (Mn) were measured. The molecular weight distribution (PDI = Mw / Mn) was calculated from this measured value.

(Amine number)
The amine value represents the mass of potassium hydroxide (KOH) equivalent to the basic component per gram of solid content. The measurement sample was dissolved in tetrahydrofuran, and the obtained solution was subjected to neutralization titration 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 using 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) w: mass (g) of measurement sample (solid content conversion)

(Acid value)
The acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content. The measurement sample was dissolved in tetrahydrofuran, a few drops of phenolphthalein ethanol solution was added as an indicator, and neutralization titration was performed 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 used for titration (mL)
f: Potency of 0.1 mol / L potassium hydroxide / ethanol solution w: Mass (g) of measurement sample (solid content conversion)

(Formaldehyde amount)
A sample (0.5 g) was injected into 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 allowed to stand at room temperature for 2 hours.
It was washed out with 4 mL of acetonitrile and made up 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 / ultra pure water = 65: 35 solution, column temperature : 40 ° C., flow rate: 1.0 mL / min, detection wavelength: 360 nm), and using two kinds 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.

(Initial viscosity)
Using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.), a cone rotor (1 ° 34 ′ × R24) was used, and the viscosity was measured at 25 ° C. and a rotor rotational speed of 60 rpm. The measurement was performed on the colored composition stored at 25 ° C. for 2 hours after preparation.

(Initial particle size)
The particle size was measured at 25 ° C. using a concentrated particle size analyzer (trade name: FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.). The measurement was performed on the colored composition stored at 25 ° C. for 2 hours after adjustment. Samples were diluted with propylene glycol monomethyl ether acetate (PGMEA) as needed.

(Luminance)
The luminance was measured on an uncured dry coating film before and after heat treatment. By measuring the luminance before and after the heat treatment, the degree of discoloration caused by the heat treatment was evaluated.
Three coating films of pigment dispersion compositions having different thicknesses are formed on a glass plate (50 mm × 50 mm) whose surface has been cleaned, using a spin coater (trade name: MS-A100, manufactured by Mikasa). Dry at 10 ° C. for 10 minutes. The dried coating film was measured for x and Y values using a spectrocolorimeter (trade name: CM-5, manufactured by Konica Minolta). A calibration curve was created from the obtained x and Y values, and a corrected Y value (before heat treatment) when x = 0.640 was calculated.
Next, the coating film was heat-treated at 230 ° C. for 30 minutes, and the corrected Y value (after heat treatment) was calculated in the same manner as described above. Further, ΔY was calculated from the corrected Y value before and after the heat treatment.

<Manufacture of block copolymer>
PCL5 (299.2 g), BMA (99.8 g), AIBN (2.462 g), and PMA (266.0 g) were charged into a flask equipped with an argon gas introduction tube and a stirrer, and after substitution with argon, BTEE (22. 48g) and DBDT (13.84g) were added and reacted at 60 ° C for 15 hours. The polymerization rate was 99%.

  To the obtained solution, a mixed solution of DMAEMA (125.8 g), AIBN (0.822 g), and PMA (83.9 g) previously substituted with argon was added and reacted at 60 ° C. for 15 hours. The polymerization rate was 99%.

  After completion of the reaction, the reaction solution was poured into n-heptane which was being stirred. The precipitated polymer was suction filtered and dried to obtain a block copolymer. The obtained block copolymer had an Mw of 15,600, a PDI of 1.49, and an amine value of 83 mgKOH / g. In addition, the content rate of each structural unit in a block copolymer was computed from the preparation ratio of the vinyl monomer used for polymerization reaction, and the polymerization rate of a vinyl monomer.

<Preparation of dispersant composition>
Dispersant composition No. A
To a flask equipped with a stirrer, 87.5 g of a block copolymer, 7.96 g of TIDP, and 71.6 g of PMA were added and mixed.

Dispersant composition No. B ~ H
Dispersant composition No. In the same manner as in the adjustment method of A, the raw materials were mixed so that the blending composition shown in Table 1 was obtained. B to H were obtained.

ＴＩＤＰ：亜リン酸トリイソデシル
ＴＢＰ：亜リン酸トリブチル
ＴＰＰ：亜リン酸トリフェニル
ＢＢＣ：４、４’−ブチリデンビス（６−ｔ−ブチル−ｍ−クレゾール）
Ｉｒｇａｎｏｘ（登録商標）１０１０：ＢＡＳＦジャパン社製、ペンタエリトリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオナート］
Ｉｒｇａｆｏｓ（登録商標）１６８：ＢＡＳＦジャパン社製、亜リン酸トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）

TIDP: triisodecyl phosphite TBP: tributyl phosphite TPP: triphenyl phosphite BBC: 4,4′-butylidenebis (6-t-butyl-m-cresol)
Irganox (registered trademark) 1010: manufactured by BASF Japan, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
Irgafos (registered trademark) 168: manufactured by BASF Japan, tris phosphite (2,4-di-tert-butylphenyl)

Dispersant composition No. A to D contain a block copolymer and a phosphite represented by the formula (5). These dispersant compositions had a low formaldehyde content of 1.5 ppm or less. In particular, dispersant composition No. 1 further containing BBC (phenolic antioxidant). In B to D, formaldehyde was not detected.
Dispersant composition No. EG does not contain the phosphite represented by the formula (5). These dispersant compositions are dispersant composition No. Compared with H (only block copolymer), the amount of formaldehyde is hardly reduced.

Dispersant composition No. I
To a flask equipped with a stirrer, a polyester dispersant (AcOBu solution, solid content concentration 40% by mass), TIDP, and BBC were added and mixed so as to have the composition shown in Table 2.

Dispersant composition No. J
To a flask equipped with a stirrer, a polyester-based dispersant (AcOBu solution, solid content concentration 40% by mass) was added so as to have the composition shown in Table 2.

  Dispersant composition No. I contains a polyester dispersant and a phosphite represented by the formula (5). This dispersant composition has a low formaldehyde content of 0.7 ppm or less. The amount of formaldehyde was reduced as compared with J (polyester dispersant only).

<Synthesis of alkali-soluble resin (binder resin)>
MAA (40.0 g), BzMA (160.0 g), PMA (580.0 g) were charged into a flask equipped with an argon gas introduction tube and a stirrer, and after substitution with argon, AIBN (4.0 g), n-dodecanethiol (6.0 g) and PMA (20.0 g) were added and the temperature was raised to 90 ° C. While maintaining the solution at 90 ° C., MAA (80.0 g), BzMA (320.0 g), AIBN (8.0 g), n-dodecanethiol (12.0 g), PMA (50.0 g) were added to the solution. It was added dropwise over 1.5 hours. Sixty minutes after the completion of the dropping, the temperature was raised to 110 ° C., AIBN (0.8 g) and PMA (10.0 g) were added and reacted for 1 hour, and AIBN (0.8 g) and PMA ( 10.0 g) was added and reacted for 1 hour, and AIBN (0.8 g) and PMA (10.0 g) were further added and reacted for 1 hour.

  The resulting reaction solution was cooled to room temperature, PMA (240.0 g) was added, and an alkali-soluble resin solution having a nonvolatile content of 39.5% was obtained. The weight average molecular weight (Mw) of the alkali-soluble resin was 9,150, the molecular weight distribution (PDI) was 1.92, and the acid value was 128 mgKOH / g.

<Preparation of coloring composition>
Coloring composition No. 1
8 parts by mass of pigment, dispersant composition No. A formulation composition is prepared so that it may become 6 mass parts of A, 6 mass parts of alkali-soluble resin, and 80 mass parts of PMA, add 555 mass parts of 0.3 mm zirconia beads, and bead mill (trade name: DISPERMAT CA, VMA-GETZMANN GmbH manufactured by ) For 3 hours and sufficiently dispersed. After the dispersion was completed, the beads were filtered to obtain a colored composition. The pigment includes C.I. I. Pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals) was used. The dispersibility and luminance of the obtained colored composition were evaluated. The evaluation results are shown in Table 3.

Coloring composition No. 2-9
Except that the dispersant composition was changed, the coloring composition No. In the same manner as in the preparation method of No. 1, coloring composition No. 2-9 were prepared. The evaluation results are shown in Table 3.

Coloring composition No. 1-4 are dispersant composition No. 1 containing a phosphite represented by the formula (5) as a dispersant. Contains A to D. These colored compositions have a reduced amount of luminance before and after heat treatment. It was reduced from 8. That is, the coloring composition No. 1-4 show that the heat-resistant color-change property is excellent from the brightness | luminance of a coating film being excellent.
Coloring composition No. No. 9 is a dispersant composition No. 9 containing a polyester dispersant and a phosphite represented by the formula (5). Contains I. This colored composition has a higher luminance after heat treatment than that before heat treatment. That is, the coloring composition No. 9 shows that the heat discoloration of the coating film is excellent.
From these results, it can be expected that the luminance is improved when a color filter is produced using the colored composition of the present invention.

Claims (12)

A resinous dispersant having a tertiary amino group and a phosphite,
The dispersant composition, wherein the phosphite is a compound represented by the general formula (5).

[In General Formula (5), R ⁵¹ represents an alkyl group having 1 to 20 carbon atoms. R ⁵² and R ⁵³ each independently represents a hydrocarbon group. R ⁵² and R ⁵³ may be bonded to each other to form a cyclic structure. The compound represented by the general formula (5) may be bonded with R ⁵² or R ⁵³ to form a dimer or trimer. ]   The dispersant composition according to claim 1, wherein the content of the phosphite is 0.1 to 15 parts by mass with respect to 100 parts by mass of the resin-type dispersant.   The dispersant composition according to claim 1 or 2, wherein the resin type dispersant has an amine value of 10 mgKOH / g to 200 mgKOH / g. The resin-type dispersant is a block copolymer having an A block having a structural unit derived from a (meth) acrylic monomer and a B block having a structural unit represented by the general formula (1). The dispersing agent composition as described in any one of -3.

[In General Formula (1), R ¹¹ and R ¹² each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹³ represents a hydrogen atom or a methyl group. ]   The dispersant composition according to claim 4, wherein the block copolymer has a molecular weight distribution (PDI) of 2.5 or less.   The dispersant composition according to claim 4 or 5, wherein the block copolymer is polymerized by living radical polymerization.   The dispersant composition according to any one of claims 1 to 6, wherein the dispersant composition further contains a phenol-based antioxidant. The dispersant composition according to claim 7, 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. ^R62 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 a hydrocarbon group having 2 to 20 carbon atoms are substituted with an ester group or an ether group, or a hydrocarbon group having 1 to 20 carbon atoms. n represents the number of 1-6. However, the carbon atom bonded to the benzene ring of R ⁶¹ is a primary to tertiary carbon atom. ]   The dispersant composition according to claim 7 or 8, wherein the content of the phenolic antioxidant is 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin-type dispersant.   A coloring composition comprising the dispersant composition according to any one of claims 1 to 9, a coloring material, a binder resin, and a dispersion medium.   The coloring composition according to claim 10, which is used for a color filter.   A color filter comprising a colored layer formed using the colored composition according to claim 11.