JP7105205B2 - Dispersant composition, coloring composition, and color filter - Google Patents

Description

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

Conventionally, dyeing, printing, ink-jetting, electrodeposition, pigment dispersion, and the like are known as methods of applying colorants to substrates in the production of color filters used in liquid crystal displays and the like. Among these, the pigment dispersion method is the mainstream from the viewpoint of spectral characteristics, durability, pattern shape and accuracy. In this pigment dispersion method, a coating film made of a coloring composition mixed with a pigment, a dispersant, a dispersion medium (solvent), a binder resin, etc. is formed on a substrate, and radiation is applied through a photomask having a desired pattern. It is cured by irradiation and alkali development is carried out.

In recent years, in order to obtain good color reproducibility and high contrast of color filters, increasing the concentration of pigments in coloring compositions has been studied. When the concentration of the pigment is increased, the proportion of the dispersant is relatively decreased, so the dispersant is required to have high dispersibility (see, for example, Patent Document 1 (paragraph 0004)). Further, in alkali development, binder resins having alkali solubility play a major role. However, in the case of a pigment dispersion composition with a high concentration of pigment, the proportion of the binder resin, which is a developing component, is reduced, resulting in poor alkali developability. Therefore, the dispersant is also required to have alkali developability, which is originally required for the binder resin. As such a dispersant, in Patent Document 2, an AB block copolymer consisting of an A block having a polylactone chain in the side chain and a B block having a tertiary amino group in the side chain is used as a pigment dispersion. (See Patent Document 2 (paragraphs 0023 to 0045)).

JP 2009-265515 A JP 2013-119568 A

It has been proposed to introduce a tertiary amino group into the side chain of a resin-type dispersant in order to improve 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 in a coloring composition, formaldehyde is contained in the coloring composition. Since environmental standards have become stricter in recent years, the use of conventional resin-type dispersants causes the amount of formaldehyde in the coloring composition to fail to meet environmental standards.

In the manufacture of a liquid crystal display, after forming a colored layer pattern, a transparent electrode for driving the liquid crystal is formed thereon by vapor deposition or sputtering. An alignment film is formed. These transparent electrodes and alignment films are generally formed at a high temperature of 200° C. or higher in order to obtain sufficient performance. Here, a colored composition using a resin-type dispersant having a tertiary amino group tends to discolor in a process accompanied by high heat. Therefore, there is a problem that the luminance of the final product, the color filter, is adversely affected.

The present invention has been made in view of the above circumstances, and provides a dispersant composition that has high dispersibility of a coloring agent, generates a small amount of formaldehyde over time, and undergoes little discoloration even when exposed to high temperatures. for the purpose.

The dispersant composition of the present invention, which was able to solve the above problems, contains a resin-type dispersant having a tertiary amino group and a phosphite ester, and the phosphite ester is represented by the general formula (5) It is characterized by being a compound represented by

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

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

A resin-type dispersant having a tertiary amino group generates formaldehyde over time due to this amino group. Also, when a resin-type dispersant having a tertiary amino group is exposed to high temperatures, the tertiary amino group is oxidized and the resin-type dispersant turns yellow. Here, in the coexistence of the phosphite represented by the general formula (5), the formaldehyde generated from the resin-type dispersant and the phosphite react irreversibly. Therefore, formaldehyde in the dispersant composition can be reduced. In addition, the phosphite ester suppresses oxidation of the tertiary amino group, and can suppress yellowing of the resin-type dispersant.

The present invention also includes a coloring composition characterized by containing 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 coloring composition.

According to the present invention, it is possible to obtain a dispersant composition that has high dispersibility of a coloring agent, generates a small amount of formaldehyde over time, and undergoes little discoloration even when exposed to high temperatures.

An example of a preferred embodiment of the present invention will be described below. However, the following embodiments are merely examples. It is not limited to the following embodiments.

<Dispersant composition>
The dispersant composition of the present invention contains a resin-type dispersant having a tertiary amino group and a phosphite, wherein 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 this amino group. Also, when a resin-type dispersant having a tertiary amino group is exposed to high temperatures, the tertiary amino group is oxidized and the resin-type dispersant turns yellow. Here, in the coexistence of the phosphite represented by the general formula (5), the formaldehyde generated from the resin-type dispersant and the phosphite react irreversibly. Therefore, formaldehyde in the dispersant composition can be reduced. In addition, the phosphite ester suppresses oxidation of the amino group, and can suppress yellowing of the resin-type dispersant.

In the present invention, "(meth)acrylic" means "at least one of acrylic and methacrylic". "(Meth)acrylic monomer" refers to a monomer having a "(meth)acryloyl group" in the molecule. "(Meth)acryloyl" means "at least one of acryloyl and methacryloyl". A "vinyl monomer" refers to a monomer having a radically polymerizable carbon-carbon double bond in the molecule. A “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 to form a carbon-carbon single bond. A “structural unit derived from a vinyl monomer” refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a vinyl monomer is polymerized to form a carbon-carbon single bond.

Resin-type dispersants having a tertiary amino group include (meth)acrylic polymers, urethane polymers, polyester polymers, polyethyleneimine polymers, polyoxyethylene alkyl ether polymers, polyoxyethylene alkyl A phenyl ether-based polymer and the like can be mentioned.

The amine value of the resin-type dispersant is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 30 mgKOH/g or more, from the viewpoint of adsorption to the coloring material and coloring material dispersibility, It is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, still more preferably 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 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 represent a chain or cyclic hydrocarbon group which may have a substituent. R ¹¹ and R ¹² may combine with each other to form a cyclic structure. X ¹ represents a divalent linking group. ^R13 represents a hydrogen atom or a methyl group. ]

Various constituent components of the block copolymer will be described below.

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

The content of structural units 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 95% by mass or more, based on 100% by mass of the A block. is 100% by mass.

The (meth)acrylic monomers include (meth)acrylates having a chain alkyl group (straight-chain alkyl group or branched-chain alkyl group), (meth)acrylates having a cyclic alkyl group, and (meth)acrylates having a polycyclic structure. , (meth)acrylates having an aromatic group, (meth)acrylates having a polyalkylene glycol structural unit, (meth)acrylates having a hydroxy group, (meth)acrylates having a lactone-modified hydroxy group, (meth)acrylates having an alkoxy group Examples include acrylates, (meth)acrylates having an oxygen-containing heterocyclic group, (meth)acrylates having an acidic group, (meth)acrylic acid, and the like, and one or more of these may be used in combination. can be done.

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

The (meth)acrylate having a branched-chain alkyl group is preferably a (meth)acrylate having a branched-chain alkyl group having 1 to 20 carbon atoms in the branched-chain alkyl group, and the branched-chain alkyl group having 1 to 20 carbon atoms. (Meth)acrylates with branched alkyl groups of 10 are preferred. Examples of (meth)acrylates having a branched alkyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate and the like.

The (meth)acrylate having a cyclic alkyl group is preferably a (meth)acrylate having a cyclic alkyl group having 6 to 12 carbon atoms. Cyclic alkyl groups include cyclic alkyl groups having a monocyclic structure (eg, cycloalkyl groups). Specific examples of (meth)acrylates having a cyclic alkyl group with a monocyclic structure 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 with 6 to 12 carbon atoms. Polycyclic structures include cyclic alkyl groups having a bridged ring structure (eg, adamantyl, norbornyl, and isobornyl groups). Specific examples of (meth)acrylates having a polycyclic structure include isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-methyl-2-adamantyl (Meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate and the like.

The (meth)acrylate having an aromatic group is preferably a (meth)acrylate having an aromatic group having 6 to 12 carbon atoms. 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, an aryloxyalkyl group, and the like. Specific examples of (meth)acrylates 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, and polyethylene. Glycol (degree of polymerization = 2 to 10) propyl ether (meth) acrylate, polyethylene glycol (degree of polymerization = 2 to 10) (meth) acrylate having a polyethylene glycol structural unit such as phenyl ether (meth) acrylate; polypropylene glycol (degree of polymerization = 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 2 to 10) ethyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 2 to 10) propyl ether (meth) acrylate, polypropylene glycol (polymerization degree=2 to 10) (meth)acrylates having polypropylene glycol structural units such as phenyl ether (meth)acrylates.

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

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 preferable. The amount of caprolactone to be added is preferably 1 mol to 10 mol, 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, and 2-hydroxyethyl (meth)acrylate. 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, etc. are preferable. .

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

The (meth)acrylate having an oxygen-containing heterocyclic group is preferably a (meth)acrylate having a 4- to 6-membered oxygen-containing heterocyclic group. Specific examples of (meth)acrylates having an oxygen-containing heterocyclic group include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (3-ethyloxetan-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.

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 ), a phosphinic acid group (-- PO ₂ H ₂ ). Examples of (meth)acrylates having an acidic group include (meth)acrylates having a carboxy group, (meth)acrylates having a phosphoric acid group, and (meth)acrylates having a sulfone group.

Examples of (meth)acrylates 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 structural units other than structural units derived from (meth)acrylic monomers. Other structural units that can be contained in the A block are not particularly limited as long as they are formed from a vinyl monomer that can be copolymerized with both a (meth)acrylic monomer and a vinyl monomer that forms the B block described below. Vinyl monomers capable of forming other structural units of the A block may be used alone, or two or more of them may be used in combination.

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, vinylamides, vinyl carboxylates, and dienes. These vinyl monomers may have a hydroxy group and an epoxy group.

α-olefins include 1-hexene, 1-octene, 1-decene and the like.
Examples of aromatic vinyl monomers include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene and the like.
Vinyl monomers containing a heterocycle include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 2-vinylpyridine, 4-vinylpyridine, N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide and the like. mentioned.
Vinylamides include N-vinylformamide, N-vinylacetamide, 1-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam and the like.
Vinyl carboxylate includes 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 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 a high affinity with the dispersion medium and the binder resin, and the alkali developability of the block copolymer. 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 to 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 1-7, more preferably an integer of 1-5.

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 methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, 1-methylethylene group and the like. 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 methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, A nonamethylene group, a decamethylene group, and the like can be mentioned. R ³ is preferably an alkylene group having 1 to 8 carbon atoms, 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 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 even more preferably 85% by mass or less. By setting the content 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, the solubility in an alkaline developer is increased, and the alkaline developability can be improved. However, if the ratio is high, there is a possibility that the affinity with the solvent and the alkali-soluble resin will be lowered. Therefore, the ratio of the structural units derived from the vinyl monomer having an acidic group is preferably such that the overall acid value of the block copolymer is lower than the amine value.

When a structural unit derived from a vinyl monomer having an acidic group is contained, the content thereof is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more in 100% by mass of the A block. , preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 16% by mass or less. If the content of the structural unit derived from a vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate becomes faster when neutralized with alkali in alkaline development, and if it is 20% by mass or less, hydrophilicity is high. Therefore, it is possible to prevent the formed pixels from becoming disorderly.

The A block contains less than 5% by mass, preferably 3% by mass or less, more preferably 1% by mass or less of a structural unit represented by the general formula (1) described later, and in the general formula (1) It is more preferable not to contain the represented structural unit. The lower the content of the structural unit represented by formula (1) in the A block, the better the dispersibility of the coloring material.

The A block preferably has no amino group. In other words, 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, the colorant is adsorbed to both the A block and the B block when used as a dispersant, resulting in a decrease in the dispersibility of the colorant. The content of structural units derived from a vinyl monomer 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 0.1% by mass or less, most preferably 0% by mass.

When two or more types of structural units are contained in the A block, the various structural units contained in the A block may be contained in any form of random copolymerization, block copolymerization, or the like in the A block. , it is preferably contained in the form of random copolymerization from the viewpoint of uniformity. For example, the A block may be formed of a copolymer of a structural unit consisting of the a1 block and a structural unit consisting of the a2 block.

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

(Structural unit represented by general formula (1))
The structural unit represented by general formula (1) may be of one kind or may be of two or more kinds. By using the structural unit represented by the general formula (1), the adsorbability to the coloring material is high, and the heat resistance can be increased.

［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 represent a chain or cyclic hydrocarbon group which may have a substituent. R ¹¹ and R ¹² may combine with each other to form a cyclic structure. X ¹ represents a divalent linking group. ^R13 represents a hydrogen atom or a methyl group. ]

Examples of the chain hydrocarbon groups represented by R ¹¹ and R ¹² include straight-chain alkyl groups and branched-chain alkyl groups. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. 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 and n-lauryl group. is mentioned. The branched-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms. Examples of the branched chain alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, neopentyl group and isooctyl group.

Examples of substituents of the chain hydrocarbon groups represented by R ¹¹ and R ¹² include halogen groups, alkoxy groups, benzoyl groups (--COC ₆ H ₅ ), and hydroxy groups.

The cyclic hydrocarbon groups represented by R ¹¹ and R ¹² include cyclic alkyl groups and aromatic groups, and the cyclic alkyl groups and aromatic groups may have a chain portion. The number of carbon atoms in the cyclic alkyl group is preferably 4 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The aromatic group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms. Examples of the aromatic group include a phenyl group, a tolyl group, a xylyl group, and a mesityl group. Examples of the chain portion of the cyclic alkyl group having a chain portion and the chain portion of the 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 a carbon Examples include alkylene groups of numbers 1 to 3.

Examples of substituents of the cyclic hydrocarbon groups represented by R ¹¹ and R ¹² include halogen groups, alkoxy groups, chain alkyl groups, and hydroxy groups.

Examples of the cyclic structure formed by combining R ¹¹ and R ¹² include a 5- to 7-membered nitrogen-containing hetero ring or a condensed ring formed by condensing two of these. The nitrogen-containing heterocyclic ring preferably has no aromaticity, 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), the divalent linking group X ¹ includes, for example, 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 - group and/or -COO-R ¹⁶ - group, more preferably -COO-R ¹⁶ - group. Although the bonding direction of the amide group and the ester group is not particularly limited, 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 --OR 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 a 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, more preferably is an alkylene group having 1 to 4 carbon atoms. Specific examples include a 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 formula (1) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, diethylaminoethyl (meth)acrylate, ) 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 in 100% by mass of the B block, and is 98% by mass. % or less, more preferably 80 mass % or less, and even more preferably 70 mass % or less. By setting the content of the structural unit represented by the general formula (1) within this range, it is considered to have a high affinity with the coloring material.

The B block may have a structural unit represented by general formula (2). The structural unit represented by general formula (2) in the B block may be of only one type, or may be of two or more types. If the B block has a structural unit represented by general formula (2), strong adsorption to the coloring material surface can be maintained for a long period of time, and 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 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 combine with each other to form a cyclic structure. X ² represents a divalent linking group. ^R24 represents a hydrogen atom or a methyl group. Y ⁻ represents a counterion. ]

Examples of the chain hydrocarbon groups represented by R ²¹ to R ²³ include straight-chain alkyl groups and branched-chain alkyl groups. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. 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 and n-lauryl group. is mentioned. The branched-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms. Examples of the branched chain alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, neopentyl group and isooctyl group.

Examples of substituents of the chain hydrocarbon groups represented by R ²¹ to R ²³ include halogen groups, alkoxy groups, benzoyl groups (--COC ₆ H ₅ ), and hydroxy groups.

The cyclic hydrocarbon groups represented by R ²¹ to R ²³ include cyclic alkyl groups and aromatic groups, and the cyclic alkyl groups and aromatic groups may have a chain portion. The number of carbon atoms in the cyclic alkyl group is preferably 4 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. The aromatic group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms. Examples of the aromatic group include a phenyl group, a tolyl group, a xylyl group, and a mesityl group. Examples of the chain portion of the cyclic alkyl group having a chain portion and the 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 a carbon Examples include alkylene groups of numbers 1 to 3.

Examples of substituents possessed by the cyclic hydrocarbon groups represented by R ²¹ to R ²³ include halogen groups, alkoxy groups, chain alkyl groups, and hydroxy groups.

Examples of the cyclic structure formed by bonding two or more of R ²¹ to R ²³ together include a 5- to 7-membered nitrogen-containing hetero ring or a condensed ring formed by condensing two of these. be done. The nitrogen-containing heterocyclic ring preferably has no aromaticity, 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), the divalent linking group X ² includes, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH—R ²⁷ — group (amide group), and a —COO—R ²⁸ — group. (ester group) and the like, preferably -CONH-R ²⁷ - and/or -COO-R ²⁸ -, more preferably -COO-R ²⁸ -. Although the bonding direction of the amide group and the ester group is not particularly limited, 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—OR 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, more preferably is an alkylene group having 1 to 4 carbon atoms. Specific examples include a 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 a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.

Y ⁻ includes halogen anions, alkylcarboxylate anions, nitroxide anions, alkylsulfate anions, sulfonate anions, phosphate anions, alkylphosphate anions, and the like.
Examples of the halogen anions include fluoroanions, chloroanions, bromoanions, and iodine anions.
Examples of the alkyl carboxylate anions include alkyl carboxylate anions such as acetate anions and propionate anions; and aromatic carboxylate anions such as benzoate anions.
Examples of the sulfate anion include alkyl sulfate anions such as methyl sulfate anion and ethyl sulfate anion; and aromatic sulfate anions such as phenyl sulfate anion and benzyl sulfate anion.
Examples of the sulfonate anion include alkylsulfonate 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 formula (2) include (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxypropyltrimethylammonium chloride, and (meth)acryloyloxybutyltrimethylammonium chloride. , (meth)acryloyloxyethylbenzyldimethylammonium chloride, (meth)acryloyloxypropylbenzyldimethylammonium chloride, (meth)acryloyloxybutylbenzyldimethylammonium chloride, (meth)acryloyloxyethylbenzyldiethylammonium chloride, (meth)acryloyloxy Propylbenzyldiethylammonium chloride, (meth)acryloyloxybutylbenzyldiethylammonium chloride, (meth)acryloylamidopropylbenzyldimethylammonium chloride, (meth)acryloyloxyethyltrimethylammonium bromide, (meth)acryloyloxypropyltrimethylammonium bromide, (meth) ) Acryloyloxybutyltrimethylammonium bromide, (meth)acryloyloxyethylbenzyldimethylammonium bromide, (meth)acryloyloxypropylbenzyldimethylammonium bromide, (meth)acryloyloxybutylbenzyldimethylammonium bromide, (meth)acryloyloxyethylbenzyldiethylammonium Bromide, (meth)acryloyloxypropylbenzyldiethylammonium bromide, (meth)acryloyloxybutylbenzyldiethylammonium bromide, (meth)acryloylamidopropylbenzyldimethylammonium bromide, (meth)acryloyloxyethyltrimethylammonium iodide, (meth)acryloyl Oxypropyltrimethylammonium iodide, (meth)acryloyloxybutyltrimethylammonium iodide, (meth)acryloyloxyethylbenzyldimethylammonium iodide, (meth)acryloyloxypropylbenzyldimethylammonium iodide, (meth)acryloyloxybutylbenzyldimethylammonium iodide ammonium iodide, (meth)acryloyloxyethylbenzyldiethylammonium iodide, (meth)acryloyloxypropylbenzyldiethylammonium iodide, (Meth)acryloyloxybutylbenzyldiethylammonium iodide, (meth)acryloyloxyethyltrimethylammonium fluoride, (meth)acryloyloxypropyltrimethylammonium fluoride, (meth)acryloyloxybutyltrimethylammonium fluoride, (meth)acryloyloxy Ethylbenzyldimethylammonium fluoride, (meth)acryloyloxypropylbenzyldimethylammonium fluoride, (meth)acryloyloxybutylbenzyldimethylammonium fluoride, (meth)acryloyloxyethylbenzyldiethylammonium fluoride, (meth)acryloyloxypropylbenzyl Diethylammonium fluoride, (meth)acryloyloxybutylbenzyldiethylammonium fluoride, (meth)acryloyloxyethyltrimethylammonium methyl sulfate, (meth)acryloyloxypropyltrimethylammonium methylsulfate, (meth)acryloyloxybutyltrimethyl ammonium = methylsulfate, (meth) acryloyloxyethyldimethylethylammonium = ethylsulfate, (meth)acryloyloxypropyldimethylethylammonium = ethylsulfate, (meth)acryloyloxypropyldimethylethylammonium = ethylsulfate, (meth) ) acryloyloxyethyltrimethylammonium = toluene-4-sulfonate, (meth)acryloyloxypropyltrimethylammonium = toluene-4-sulfonate, (meth)acryloyloxybutyltrimethylammonium = toluene-4-sulfonate, (meth)acryloylamidopropyltrimethyl ammonium=methylsulfate, (meth)acryloylamidopropylethyldimethylammonium=ethylsulfate and the like.

When the structural unit represented by the general formula (2) is contained, the content thereof is preferably 2% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more in 100% by mass of the B block. , preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less. By setting the content of the structural unit represented by the general formula (2) within this range, it is believed to have a high affinity with the coloring material.

The B block may contain only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may contain 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 mass of the B block. %, 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 the B block does not substantially contain a structural unit derived from a vinyl monomer having an acidic group. That is, the content of the structural unit derived from the vinyl monomer having an acidic group is preferably 5% by mass or less, more preferably 2% by mass or less, in 100% by mass of the B block.

Specific examples of the vinyl monomer that can form other structural units of the B block are the same as the specific examples of the vinyl monomer that can form other structural units 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 manner such as random copolymerization or block copolymerization in the B block. , it is preferably contained in the form of random copolymerization from the viewpoint of uniformity. For example, the B block may be formed of a copolymer of a structural unit consisting of the b1 block and a structural unit consisting of the 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), but 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, the group consisting of (AB) _m type, (AB) _m - A type, (B-A) _m - B type (m is an integer of 1 or more, for example, an integer of 1 to 3) A copolymer having at least one structure selected from is preferred. Among these, AB type diblock copolymers are preferred from the viewpoint of handling during processing and physical properties of the composition. By forming an 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 coloring agent, the dispersing medium (solvent), and the binder resin (alkali-soluble resin) can act efficiently and favorably. The block copolymer may have blocks 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, based on 100% by mass of the entire block copolymer. More preferably 80% by mass or less, still more preferably 75% by 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, based on 100% by mass of the entire block copolymer. More preferably 60% by mass or less, still more preferably 55% by mass or less. By adjusting the content of the A block and the B block within the above range, the dispersing performance is further improved when used as a dispersant.

The mass ratio of the A block and the B block (A block/B block) in the block copolymer is preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, and 95 /5 or less, more preferably 90/10 or less, and still more preferably 80/20 or less. If the mass ratio of the A block and the B block is within the above range, the dispersing 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 a 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 even 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. Above, more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by 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, and particularly preferably 6,000 or more. 000 or less, more preferably 30,000 or less, still more preferably 25,000 or less, and particularly preferably 20,000 or less. If the weight-average molecular weight is within the above range, the dispersion performance when used as a dispersant will be better.

The molecular weight distribution (PDI) of the block copolymer is preferably 2.5 or less, more preferably 2.0 or less, and even 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 width of the molecular weight distribution, the more uniform the molecular weight of the copolymer. When the value is 1.0, the narrowest molecular weight distribution. That is, the lower limit of PDI is 1.0. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.5, it includes those with small molecular weights and those with large molecular weights.

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 viewpoint of adsorption to the coloring material and coloring material dispersibility, It is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, still more preferably 100 mgKOH/g or less.

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

(Method for producing block copolymer)
As a method for producing the block copolymer, the A block is first produced by the polymerization reaction of the vinyl monomer, and the B block is polymerized on the A block; A method of polymerizing block monomers; a method of separately producing blocks A and B and then coupling the blocks A and B;

Although the polymerization method is not particularly limited, living radical polymerization is preferred. That is, the block copolymer is preferably polymerized by living radical polymerization. In the conventional radical polymerization method, not only initiation reaction and propagation reaction but also termination reaction and chain transfer reaction cause deactivation of propagating terminal, and tend to result in a mixture of polymers with various molecular weights and non-uniform compositions. On the other hand, the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method. It is preferable in that it is easy to precisely control and manufacture a polymer with a uniform composition.

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

The TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent. 2004/072126 and methods described in WO 2004/096870.

Specific polymerization methods for the TERP method include the following (a) to (d).
(a) A vinyl monomer is polymerized using an organic tellurium compound represented by general formula (3).
(b) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by general formula (3) and an azo polymerization initiator.
(c) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by general formula (3) and an organic ditelluride compound represented by general formula (4).
(d) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by general formula (3), an azo polymerization initiator, and an organic ditelluride compound represented by 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 general formula (4), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. ]

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 specific examples are as follows.
Examples of alkyl groups 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 and heptyl. linear or branched alkyl groups such as radicals, octyl groups, and cyclic alkyl groups such as cyclohexyl groups. A linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
A phenyl group, a naphthyl group, etc. can be mentioned as an aryl group.
A pyridyl group, a furyl group, a thienyl group, etc. can be mentioned as an aromatic heterocyclic 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 specific examples of each group are as follows.
Examples of alkyl groups 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 and heptyl. linear or branched alkyl groups such as radicals, octyl groups, and cyclic alkyl groups such as cyclohexyl groups. A linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

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 It is a propargyl group, specifically as follows.
Examples of alkyl groups 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 and heptyl. linear or branched alkyl groups such as octyl groups, cyclic alkyl groups such as cyclohexyl groups, and the like. A linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
A phenyl group, a naphthyl group, etc. can be mentioned as an aryl group. A phenyl group is preferred.
Examples of the substituted aryl group include a phenyl group having a substituent, a naphthyl group having a substituent, and the like. Examples of the substituents of the aryl group having the above-mentioned substituents include halogen atoms, hydroxy groups, alkoxy groups, amino groups, nitro groups, cyano groups, and carbonyl-containing groups represented by —COR ³⁴¹ (R ³⁴¹ is a carbon 1-8 alkyl groups, aryl groups, C1-8 alkoxy groups or aryloxy groups), sulfonyl groups, trifluoromethyl groups and the like. Moreover, it is preferable that one or two of these substituents are substituted.
A pyridyl group, a furyl group, a thienyl group, etc. can be mentioned as an aromatic heterocyclic group.
The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom. butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.
Acyl groups include acetyl, propionyl, and benzoyl groups.
Examples of amide groups 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).
The oxycarbonyl group is preferably 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), such as a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, 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 and ethoxycarbonyl groups.
The allyl group includes -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 , each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and each substituent may be connected in a cyclic structure).
The propargyl group includes —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 or an alkyl group having 1 to 8 carbon atoms , an aryl group or a silyl group) and the like.

Specifically, the organic tellurium compound represented by the general formula (3) is (methyltheranylmethyl)benzene, (methyltheranylmethyl)naphthalene, ethyl-2-methyl-2-methyltheranyl-propionate, ethyl-2- methyl-2-n-butyltheranyl-propionate, (2-trimethylsiloxyethyl)-2-methyl-2-methyltheranyl-propionate, (2-hydroxyethyl)-2-methyl-2-methyltheranyl-propionate or (3-trimethylsilylpropargyl )-2-methyl-2-methylteranyl-propionate, etc., organic All tellurium compounds can be exemplified.

Specific examples of the organic ditelluride compound represented by the general formula (4) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, di -n-butyl ditelluride, di-s-butyl ditelluride, di-t-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis-(p-methoxyphenyl) ditelluride, bis-(p-aminophenyl) ditelluride, bis -(p-nitrophenyl)ditelluride, bis-(p-cyanophenyl)ditelluride, bis-(p-sulfonylphenyl)ditelluride, dinaphthylditelluride, dipyridylditelluride and the like can be exemplified.

As the azo polymerization initiator, any azo polymerization initiator that is commonly used in radical polymerization can be used without any particular limitation. 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)propane], 2 , 2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2′-azobis(2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2 , 2′-azobis(N-butyl-2-methylpropionamide) or 2,2′-azobis(N-cyclohexyl-2-methylpropionamide).

The polymerization step is carried out in a vessel purged with an inert gas, with a vinyl monomer and an organic tellurium compound of general formula (3) for the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution, etc., depending on the type of the vinyl monomer, and further adding an azo A system polymerization initiator and/or an organic ditelluride compound of general formula (4) is mixed. At this time, examples of the inert gas include nitrogen, argon, and helium. Argon and nitrogen are preferred.

The amount of the vinyl monomer used in (a), (b), (c) and (d) may be appropriately adjusted according to the physical properties of the intended copolymer. It is preferable to use 5 mol to 10000 mol of the vinyl monomer per 1 mol of the organic tellurium compound of general formula (3).

When the organic tellurium compound represented by the general formula (3) and the azo polymerization initiator (b) are used in combination, 0.01 mol to 10 mol of the azo polymerization initiator is used per 1 mol of the organic tellurium compound represented by the general formula (3). It is preferable to

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

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

The polymerization reaction can be carried out without a solvent, but may be carried out by using an aprotic or protic solvent generally used in radical polymerization and stirring the mixture. Aprotic solvents that can be used are, for example, anisole, benzene, toluene, N,N-dimethylformamide (DMF), dimethylsulfoxide (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 protic solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol and diacetone alcohol.

The amount of the solvent to be 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 per 1 g of the vinyl monomer. It is preferably 10 ml or less, more preferably 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 resulting copolymer, but the mixture is usually stirred at 0°C to 150°C for 1 minute to 100 hours. The TERP method can obtain high yields and precise molecular weight distributions even at low polymerization temperatures and short polymerization times. At this time, the pressure is usually normal pressure, but may be pressurized or reduced.

After completion of the polymerization reaction, the desired copolymer can be separated from the resulting reaction mixture by removing the used solvent, residual vinyl monomers, and the like by ordinary separation and purification means.

The growing terminal of the copolymer obtained by the polymerization reaction is in the form of —TeR ³¹ (wherein R ³¹ is the same as above) derived from the tellurium compound, and is deactivated by an operation in air after the completion of the polymerization reaction. However, tellurium atoms may remain. Since a copolymer having a tellurium atom remaining at the end thereof is colored or has poor thermal stability, it is preferable to remove the tellurium atom.

Methods for removing tellurium atoms include radical reduction methods using tributylstannane or thiol compounds; adsorption methods using activated carbon, silica gel, activated alumina, activated clay, molecular sieves, polymer adsorbents, etc.; ion exchange resins, etc. Method of adsorbing metals: Hydrogen peroxide solution or peroxides such as benzoyl peroxide are added, air or oxygen is blown into the system to oxidize and decompose the tellurium atoms at the ends of the copolymer, washing with water or appropriate A liquid-liquid extraction method or solid-liquid extraction method that removes residual tellurium compounds by combining solvents; a purification method in a solution state such as ultrafiltration that extracts and removes only those with a specific molecular weight or less can be used. , or a combination of these methods can be used.

When the tertiary amine group of the structural unit represented by formula (1) is quaternized, quaternizing agents include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide; benzyl chloride; , benzyl bromide, benzyl iodide and other aralkyl halides; 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 include aromatic alkyl sulfonates such as ethyl. Among these, 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, and p-toluenesulfone are preferred. Aromatic alkyl sulfonates such as ethyl acetate, more preferably benzyl chloride, dimethyl sulfate and methyl p-toluenesulfonate. Alkyl groups and aralkyl groups derived from the quaternizing agent are introduced into the structure after quaternization. Therefore, the amount of the structural unit represented by formula (2) can be estimated by measuring the amounts of the alkyl groups and aralkyl groups introduced by quaternization.

As a method for quaternizing a part of the tertiary amine structure of the structural unit represented by formula (1) in the polymer, there is a method of contacting the polymer with a quaternizing agent. Specifically, a method of polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit represented by formula (1), adding a quaternizing agent to the reaction solution, and stirring the reaction solution may be mentioned. . 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. is. It is also preferable to dilute the reaction solution after polymerization when adding the quaternizing agent. Examples of the solvent added for dilution include a solvent that can be used in the polymerization reaction, a protic solvent, and a mixed solvent of a solvent used in the polymerization reaction and a protic solvent. It can be selected as appropriate. Methanol is more preferred as the protic solvent.

(phosphite ester)
The dispersant composition of the present invention contains a phosphite represented by general formula (5). Formaldehyde generated from the resin-type dispersant can be reduced by containing the phosphite ester. In addition, when the resin-type dispersant is exposed to high temperature, oxidation of amino groups can be suppressed, and yellowing of the dispersant composition can be suppressed. The phosphites represented by the general formula (5) may be used singly or in combination of two or more.

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

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

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

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

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

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

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

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

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

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

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

The phosphite ester represented by the general formula (5) contained in the dispersant composition may be of one kind or may be of a plurality of kinds. In the dispersant composition, the content of the phosphite ester represented by general formula (5) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass, with respect to 100 parts by mass of the resin-type dispersant. It is at least 1.0 parts by mass, more preferably at least 1.0 parts by mass, preferably at most 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 (phosphite/amino group) between the tertiary amino group possessed by the resin-type dispersant and the phosphite represented by the general formula (5) is 0.001. It is preferably 0.005 or more, still more preferably 0.01 or more, and preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.2 or less. If the said molar ratio is in the said range, the reduction effect of formaldehyde and the yellowing suppression effect of a dispersing agent composition will improve more. Moreover, when the molar ratio exceeds 0.5, the viscosity of the dispersant composition and the coloring composition tends to increase. In addition, the amino group which a block copolymer has can be calculated from an amine value.

(Phenolic antioxidant)
The dispersant composition can 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 that the oxidative deterioration of the phosphite ester can be suppressed.

A phenolic antioxidant refers to an antioxidant having a compound having at least one hydroxy group on at least one benzene ring. Specifically, when the hydroxy group on the benzene ring is the 1-position, at least one of the 2-, 4- and 6-positions, or at least one of the 3-, 4- and 6-positions has a radical. Such a substituent that can exclude the molecule of, for example, a bulky substituent (for example, a substituent in which the carbon atom bonded to the benzene ring is a quaternary carbon atom (specific examples, t-butyl group, adamantyl group, etc.)) An antioxidant having a chemical structure having

A compound represented by the general formula (6) is preferable as the phenolic antioxidant.

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

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

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

R ⁶² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and tert-butyl group, with methyl group being preferred.

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

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

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

The phenolic antioxidant contained in the dispersant composition may be of one kind or may be of a plurality of kinds. 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, and still more preferably 1 part by mass with respect to 100 parts by mass of the resin type dispersant. 0 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2 parts by mass or less.

The mass ratio of the phosphite represented by the general formula (5) and the phenolic antioxidant contained in the dispersant composition (phenolic antioxidant/phosphite) is 0.01 or more. It is preferably 0.05 or more, still more preferably 0.1 or more, and preferably 1 or less, more preferably 0.7 or less, and still more preferably 0.5 or less. When the mass ratio is within the range, the synergistic effect with the phosphite represented by the general formula (5) can further reduce the amount of formaldehyde in the dispersant composition. Moreover, 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 dispersing medium. The dispersing medium can be appropriately selected and used as long as it disperses or dissolves the resin type dispersant and the phosphite ester, 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 monoalkyl ethers such as glycol monomethyl ether, 3-methyl-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 ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether and other glycol dialkyl ethers; 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; Glycol diacetates such as diacetate, 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; Ketones such as methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone, methoxymethylpentanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol , methoxypropanol, methoxymethylpentanol, glycerin, benzyl alcohol, etc.; n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane, etc. Hydrogens; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl; Aromatic hydrocarbons such as benzene, toluene, xylene and cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate , propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, 3-ethoxy Chain or cyclic esters such as methyl propionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; Acetonitrile and benzonitrile and nitriles such as

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 dispersing medium in the dispersant composition is usually 99% by mass. The lower limit of the content of the dispersing medium in the dispersant composition is usually 30% by mass, preferably 45% by mass, in consideration of the viscosity suitable for producing the colored composition described later.

<Coloring composition>
The coloring composition of the present invention contains the dispersant composition, a coloring material, a binder resin and a dispersion medium.

(colorant)
The type of the coloring material may be appropriately selected according to its use, and examples thereof include pigments and dyes. From the viewpoint of light resistance and heat resistance, the coloring composition preferably contains a pigment as a coloring agent. As the pigment, either an organic pigment or an inorganic pigment may be used, but an organic pigment containing an organic compound as a main component is particularly preferable. Examples of pigments include pigments of various colors such as red pigments, yellow pigments, orange pigments, blue pigments, green pigments, and purple pigments. The structure of the pigment includes azo pigments such as monoazo pigments, diazo pigments, condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, and indigo pigments. polycyclic pigments such as polycyclic pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments. The pigment contained in the coloring composition may be of only one type, or may be of a plurality of types for adjustment of chromaticity and the like.

Specific examples of pigments 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 C.I. 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 C.I. I. Orange pigments such as C.I. Pigment Orange 36, 38, 43; I. Blue pigments such as C.I. Pigment Blue 15, 15:2, 15:3, 15:4, 15:6, 16, 22, 60; 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, polyhalogenated diphenylphosphinyloxyaluminum phthalocyanine; C.I. I. Purple pigments such as Pigment Violet 23, 29, 32, 50 and the like are included. 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 preferred.

The number average particle size of the coloring material may be appropriately selected according to its use, and is not particularly limited. From the viewpoint of high transparency and high contrast, the coloring composition preferably contains a coloring material having a number average particle size of 10 nm to 150 nm.

The coloring material may contain a pigment derivative as a dispersing aid. As the dye derivative, it is preferable to contain an acidic dye derivative having an acidic group in order to ionically bond with and adsorb to the tertiary amino group and quaternary ammonium base in the resin-type dispersant. This dye derivative has an acidic functional group introduced into the dye skeleton. As the pigment skeleton, a skeleton identical or similar to that of the coloring material constituting the coloring composition, and a skeleton identical or similar to that of the compound that is the raw material of the pigment are preferable. Specific examples of the dye skeleton include an azo dye skeleton, a phthalocyanine dye skeleton, an anthraquinone dye skeleton, a triazine dye skeleton, an acridine dye skeleton, and a perylene dye skeleton. A carboxy group, a phosphoric acid group, and a sulfonic acid group are preferable as the acidic group to be introduced into the dye skeleton. A sulfonic acid group is preferred for the convenience of synthesis and for its strong acidity. The acidic group may be directly bonded to the dye skeleton, or may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, ether, sulfonamide or urethane bond. The amount of the pigment derivative to be used is not particularly limited, but it is preferably 4 parts by mass to 17 parts by mass with respect to 100 parts by mass of the colorant.

The upper limit of the content of the coloring material in the coloring composition, from the viewpoint of brightness, in the total solid content of the coloring composition is usually 80% by mass, preferably 70% by mass, and 60% by mass. is more preferable. Further, the lower limit of the content of the coloring agent 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, the solid content is a component other than the dispersion medium, which will be described later.

The content of the resin-type dispersant with respect to the coloring material in the coloring composition is preferably 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the coloring material, preferably 10 parts by mass to 100 parts by mass, It is more preferably 10 parts by mass to 80 parts by mass.

(binder resin)
The coloring composition contains a binder resin (excluding the resin type dispersant). Thereby, the alkali developability of the coloring composition and the binding property to the substrate can be improved. Although such a binder resin is not particularly limited, it is preferably a resin having an acidic group such as a carboxy group or a phenolic hydroxy group. As the binder resin, for example, for a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, at least a part of the epoxy group of the copolymer has an unsaturated monobasic Alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxy groups generated by the addition reaction, or a resin obtained by adding an acid; a linear alkali-soluble resin containing a carboxy group in the main chain resin; a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxy group portion of a carboxy group-containing resin; (meth)acrylic resin; epoxy (meth)acrylate resin having a carboxy group; They can be used singly or in combination 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 a (meth)acrylate, and styrene, a structural unit derived from a carboxy group-containing vinyl monomer and a (meth) ) random copolymers containing structural units derived from acrylates. 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-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycerol mono ( meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate and the like.

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 the (meth)acrylate is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably It is 70% by mass or more. In the binder resin, the content of the structure derived from the carboxy group-containing vinyl monomer is preferably 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 preferred, and more preferably 70% by mass or less.

Among these, random copolymers of carboxy group-containing vinyl monomers and (meth)acrylates are preferred. Specific examples of such copolymers include random copolymers of (meth)acrylic acid and butyl (meth)acrylate, random copolymers 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 affinity between the binder resin and the coloring material, the binder resin is particularly preferably a random copolymer of (meth)acrylic acid and benzyl (meth)acrylate.

In the copolymer of the carboxy group-containing vinyl monomer and (meth)acrylate, the content of (meth)acrylic acid is usually 5% to 90% by mass, and 10% to 70% by mass, based on the total monomer components. and more preferably 20% by mass to 70% by mass.

The binder resin may have a radically polymerizable carbon-carbon double bond in its side chain. By having a double bond in the side chain, the photocurability of the colored composition according to the present invention is enhanced, so that resolution and adhesion can be further improved. Examples of methods for introducing radically polymerizable carbon-carbon double bonds to side chains include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p- ) A method of reacting a compound such as vinylbenzyl glycidyl ether with the acidic group of the binder resin.

The Mw of the binder resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 5,000 to 20,000. When the Mw of the binder resin is 3,000 or more, the colored layer formed from the coloring composition has good heat resistance, film strength, etc., and when the Mw is 100,000 or less, the alkali developability of the 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, even 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 coloring 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 of only one type, or may be of 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 with respect to 100 parts by mass of the coloring material, more preferably 10 parts by mass to 100 parts by mass, 20 parts by mass parts to 80 parts by mass is more preferable.

(crosslinking agent)
The coloring composition may contain a cross-linking agent, if necessary. A cross-linking agent refers to a compound having two or more polymerizable groups. Examples of polymerizable groups include ethylenically unsaturated groups, oxiranyl groups, oxetanyl groups, N-alkoxymethylamino groups and the like. The cross-linking agent is preferably a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamino groups. The cross-linking agents can be used alone or in combination of two or more.

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

Examples of the aliphatic polyhydroxy compounds include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; of aliphatic polyhydroxy compounds. Examples of (meth)acrylates having a hydroxy group include, for example, 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, di pentaerythritol hexa(meth)acrylate, glycerol dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; pyromellitic anhydride and biphenyltetracarboxylic acid. Tetrabasic acid dianhydrides such as acid dianhydrides and benzophenonetetracarboxylic acid dianhydrides can be mentioned.

In the coloring composition, the content of the cross-linking agent is preferably 10 parts by mass to 1,000 parts by mass, particularly preferably 20 parts by mass to 500 parts by mass, based on 100 parts by mass of the coloring material. If the content of the cross-linking agent is too small, there is a possibility that sufficient curability cannot be obtained. On the other hand, if the amount of the cross-linking agent is too large, the colored composition of the present invention will have reduced alkali developability, and scumming, film residue, etc. tend to occur easily on the substrate or on the light-shielding layer in the unexposed area. .

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

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

In the coloring composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, relative to 100 parts by mass of the cross-linking agent. In this case, if the content of the photopolymerization initiator is too low, curing by exposure may be insufficient.

(dispersion medium)
The coloring composition contains a dispersing medium. The dispersion medium can be appropriately selected and used as long as it disperses or dissolves other components constituting the coloring composition, does not react with these components, and has moderate volatility. For example, conventionally known organic solvents can be used, and examples thereof include organic solvents that can be used in the dispersant composition. The organic solvent is preferably glycol alkyl ether acetates, monohydric or polyhydric alcohols, from the viewpoint of dispersibility of pigments, solubility of dispersants, applicability of pigment dispersion compositions, and the like. The solvent contained in the pigment dispersion composition may be of one kind or may be of a plurality of kinds.

When forming pixels of a color filter by photolithography, the boiling point of the dispersion medium is preferably 100° C. to 200° C. (under a pressure of 1013.25 hPa. Hereinafter, all boiling points are the same.), and 120° C. to 170° C. is preferable. more preferred. Among the above dispersion media, glycol alkyl ether acetates are preferred because they have a good balance of applicability, surface tension, etc., and relatively high solubility of the constituent components in the coloring 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 a dispersing medium having such a high boiling point together, the coloring composition becomes difficult to dry, and it is possible to suppress the destruction of the interrelationship of the coloring composition due to rapid drying. 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. If the content is 3% by mass or more, it is possible to suppress the occurrence of foreign matter defects caused by the deposition and solidification of the coloring material at the tip of the slit nozzle. If it is 50% by mass or less, the drying speed of the coloring composition becomes slow, and problems such as prolonged drying time and pin marks during prebaking can be suppressed in the production of color filters described later. The dispersion medium having a boiling point of 150° C. or higher may be glycol alkyl ether acetates, and in this case, the dispersion medium having a boiling point of 150° C. or higher may not be included separately.

When forming pixels of a color filter by an inkjet method, the boiling point of the dispersion medium is preferably 130°C to 300°C, more preferably 150°C to 280°C. By setting the boiling point to 130°C or higher, the uniformity of the resulting coating film is improved. Further, by setting the boiling point to 300° C. or lower, the amount of residual solvent in the coating film after heat baking can be reduced, and defects in quality and prolonged drying time can be suppressed. In addition, the vapor pressure of the dispersion medium to be used 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 coating film to be obtained.

In the production of color filters by the inkjet method, the ink emitted from the nozzle is extremely fine, ranging from several pL to several tens of pL. tend to concentrate and dry up. 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 220° C. or higher. Further, the high-boiling solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass with respect to 100% by mass of the entire dispersion medium contained in the coloring composition The above is most preferred. By making it equal to or higher than the above lower limit, there is a tendency that the effect of preventing the solvent from evaporating from the droplets can be sufficiently exhibited.

The content of the dispersion medium in the coloring composition is not particularly limited and can be adjusted as appropriate. The upper limit of the content of the dispersing 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, preferably 80% by mass, in consideration of the viscosity suitable for application of the coloring composition. The dispersion medium can be used as a solvent for dissolving and removing precipitates formed from the coloring composition.

(Other compounding agents)
In addition to the above-described compounding agents, other compounding agents can be blended into the coloring composition as long as they do not impair the preferred physical properties of the present invention. Other compounding agents include sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, plasticizers, organic carboxylic acid compounds, organic carboxylic acid compounds, Acid anhydrides, pH adjusters, antioxidants other than the phenolic antioxidants, ultraviolet absorbers, light stabilizers, preservatives, anti-mold agents, anti-aggregation agents, adhesion improvers, development improvers, storage stability agent etc. can be mentioned.

Sensitizing dyes include 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)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)1,3,4-thiadiazole, ( p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc. are mentioned.

Thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like.

Nonionic surfactants include fluorine surfactants (1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetra fluorooctylhexyl 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.), silicone surfactants, polyoxyethylene surfactants Agents (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, pentaerythrityl fatty acid esters, polyoxyethylene pentaerythrityl fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, etc.) mentioned.
Examples of anionic surfactants include alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene alkylethersulfonates, alkylsulfates, alkylsulfates, higher alcohol sulfates, aliphatic Alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special polymer surfactants agents and the like.
Cationic surfactants include quaternary ammonium salts, imidazoline derivatives, alkylamine salts and the like.
Amphoteric surfactants include betaine type compounds, imidazolium salts, imidazolines, amino acids and the like.

Examples of plasticizers 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 monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid and methacrylic acid, oxalic acid, malonic acid, succinic acid and 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, carboxylic acids in which a carboxyl group is bonded to a phenyl group via a carbon bond, and the like.

Organic carboxylic anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2- cyclohexenedicarboxylic acid, n-octadecylsuccinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride and the like.

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

<Color filter>
The color filter of the present invention comprises a colored layer formed using the coloring composition.

Examples of methods for manufacturing color filters include the following methods. Thermosetting resin sheets such as thermoplastic resin sheets such as polyester resin, polyolefin resin, polycarbonate resin and polymethyl methacrylate resin, epoxy resin, unsaturated polyester resin and poly(meth)acrylic resin, various types of glass After applying the coloring composition of the present invention in which a red pigment is dispersed, for example, on a transparent substrate such as the above, prebaking is performed to evaporate the solvent (dispersion medium) to form a coating film. Next, after exposing this coating film through a photomask, it is developed using an alkaline developer (such as an aqueous solution containing an organic solvent or a surfactant and an alkaline compound) to dissolve and remove the unexposed areas of the coating film. do. After that, post-baking is performed to form a pixel array in which a red pixel pattern is arranged in a predetermined arrangement. Next, using each green or blue coloring composition, each coloring composition is applied, pre-baked, exposed, developed and post-baked in the same manner as described above to form a green pixel array and a blue pixel array on the same substrate. Form on top. As a result, a color filter is obtained in which a pixel array of the three primary colors of red, green and blue is arranged on the substrate. However, in the present invention, the order of forming pixels of each color is not limited to the above.

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

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

The color filter of the present invention has high dimensional accuracy and can be suitably used for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is by no means limited to the following examples, and can be modified as appropriate without changing the gist of the invention. The polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI), amine value and acid value of the block copolymer and binder resin, and the dispersibility, brightness and amount of formaldehyde of the coloring composition are determined by the following methods. was evaluated according to

Abbreviations have the following meanings.
PCL5: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (manufactured by Daicel Chemical Industries, Ltd., Plaxel (registered trademark) FM5)
BMA: butyl methacrylate DMAEMA: dimethylaminoethyl methacrylate MAA: methacrylic acid BzMA: benzyl methacrylate BTEE: ethyl-2-methyl-2-n-butyltheranyl-propionate DBDT: dibutyl ditelluride AIBN: 2,2'-azobis(isobutyl lonitrile)
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) spectrometer (manufactured by Bruker Biospin, model: AVANCE500 (frequency: 500 MHz)). . With respect to the obtained NMR spectrum, the integration ratio of the peaks of the monomer-derived vinyl group and the polymer-derived ester side chain peak was determined to calculate the polymerization rate of the monomer.

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))
It was determined by gel permeation chromatography (GPC) using a high-performance liquid chromatograph (manufactured by Tosoh, model HLC-8320). One column 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 in the mobile phase, differential refractometer in the detector It was used. The measurement conditions were a column temperature of 40° C., a sample concentration of 10 mg/mL, a sample injection volume of 10 μm, and a flow rate of 0.2 mL/min. Polystyrene (molecular weight 427,000, 190,000, 96,400, 37,400, 10,200, 2,630, 906) is used as a standard substance to create a calibration curve (calibration curve), and the weight average molecular weight ( Mw) and number average molecular weight (Mn) were measured. A molecular weight distribution (PDI=Mw/Mn) was calculated from this measured value.

(amine value)
The amine number represents the mass of potassium hydroxide (KOH) equivalent to the basic component per gram of solid content. A measurement sample was dissolved in tetrahydrofuran, and the resulting solution was neutralized and titrated with a 0.1 mol/L hydrochloric acid/2-propanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). Using the inflection point of the titration pH curve as the titration end point, the amine value (B) was calculated by the following formula.
B = 56.11 x Vs x 0.1 x f/w
B: amine value (mgKOH/g)
Vs: Amount (mL) of 0.1 mol/L hydrochloric acid/2-propanol solution required for titration
f: 0.1 mol/L hydrochloric acid (2-propanolic) titer w: Mass (g) of measurement sample (in terms of solid content)

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

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

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

(Initial particle size)
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 preparation. Samples were diluted with propylene glycol monomethyl ether acetate (PGMEA) as needed.

(Luminance)
Brightness measurements were performed on uncured dry coatings before and after heat treatment. By measuring the brightness before and after the heat treatment, the degree of discoloration caused by the heat treatment was evaluated.
On a surface-washed glass plate (50 mm × 50 mm), a spin coater (trade name: MS-A100, manufactured by Mikasa) was used to form three coating films of a pigment dispersion composition with different thicknesses. C. for 10 minutes. The x and Y values of the dried coating film were measured with a spectrophotometer (trade name: CM-5, manufactured by Konica Minolta). A calibration curve was created from the obtained x and Y values, and the corrected Y value (before heat treatment) at 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 above. Also, ΔY was calculated from the corrected Y values before and after the heat treatment.

<Production 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 inlet tube and a stirrer, and after purging with argon, BTEE (22. 48 g) and DBDT (13.84 g) were added and reacted at 60° C. for 15 hours. The polymerization rate was 99%.

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

After completion of the reaction, the reaction solution was poured into stirring n-heptane. A block copolymer was obtained by filtering the precipitated polymer with suction and drying it. The resulting block copolymer had an Mw of 15,600, a PDI of 1.49 and an amine value of 83 mgKOH/g. The content of each structural unit in the block copolymer was calculated from the charging ratio of the vinyl monomer used in the polymerization reaction and the polymerization rate of the vinyl monomer.

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

Dispersant Composition No. B-H
Dispersant Composition No. In the same manner as in the preparation method of A, the raw materials were mixed so as to have the composition shown in Table 1, and dispersant composition No. 1 was prepared. 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 (2,4-di-tert-butylphenyl) phosphite

Dispersant Composition No. A to D contain a block copolymer and a phosphite represented by formula (5). These dispersant compositions had a low formaldehyde content of 1.5 ppm or less. In particular, dispersant composition no. No formaldehyde was detected in BD.
Dispersant Composition No. E to G do not contain the phosphite represented by formula (5). These dispersant compositions are dispersant composition no. Compared to H (block copolymer only), the amount of formaldehyde is hardly reduced.

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

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

Dispersant Composition No. I contains a polyester-based dispersant and a phosphite represented by formula (5). This dispersant composition has a small amount of formaldehyde of 0.7 ppm or less, and dispersant composition No. The amount of formaldehyde was reduced compared to J (polyester-based dispersant only).

<Synthesis of alkali-soluble resin (binder resin)>
Argon gas inlet tube, put MAA (40.0 g), BzMA (160.0 g), PMA (580.0 g) in a flask equipped with a stirrer, after argon substitution, 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., add MAA (80.0 g), BzMA (320.0 g), AIBN (8.0 g), n-dodecanethiol (12.0 g), PMA (50.0 g) to the solution. It was added dropwise over 1.5 hours. After 60 minutes from the completion of dropping, the temperature was raised to 110° C., AIBN (0.8 g) and PMA (10.0 g) were added and allowed to react for 1 hour, and further AIBN (0.8 g) and PMA ( 10.0 g) was added and allowed to react for 1 hour, then AIBN (0.8 g) and PMA (10.0 g) were added and allowed to react 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 non-volatile 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: 6 parts by mass, 6 parts by mass of alkali-soluble resin, and 80 parts by mass of PMA. ) for 3 hours to fully disperse. After completion of dispersion, the beads were separated by filtration to obtain a colored composition. C.I. I. Pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals) was used. The dispersibility and brightness of the resulting colored composition were evaluated. Table 3 shows the evaluation results.

Coloring composition no. 2 to 9
Colored composition No. 1 except that the dispersant composition was changed. Coloring composition No. 1 was prepared in the same manner as in the preparation method of No. 1. 2-9 were prepared. Table 3 shows the evaluation results.

Coloring composition no. 1 to 4 are dispersant composition Nos. 1 to 4 containing a phosphite represented by formula (5) as a dispersant. Contains A to D. With respect to these coloring compositions, the amount of decrease in luminance before and after heat treatment is the same as that of coloring composition No. 1. 8 was reduced. That is, coloring composition No. It can be seen that 1 to 4 are excellent in resistance to heat discoloration because the brightness of the coating film is excellent.
Coloring composition no. 9 is a dispersant composition No. 9 containing a polyester-based dispersant and a phosphite represented by formula (5). contains I. This colored composition has a higher luminance after heat treatment than before heat treatment. That is, coloring composition No. It can be seen that No. 9 is excellent in heat discoloration resistance of the coating film.
From these results, it can be expected that the luminance will be improved when a color filter is produced using the coloring composition of the present invention.

Claims (12)

containing a resin-type dispersant having a tertiary amino group and a phosphite,
A 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. ^R52 and ^R53 each independently represent a hydrocarbon group. R ⁵² and R ⁵³ may combine with each other to form a cyclic structure. The compound represented by general formula (5) may be bound at R ⁵² or R ⁵³ to form a dimer or trimer. ] 2. The dispersant composition according to claim 1, wherein the content of said phosphite ester is 0.1 to 15 parts by mass with respect to 100 parts by mass of said resin type dispersant. 3. The dispersant composition according to claim 1, wherein the resin type dispersant has an amine value of 10 mgKOH/g to 200 mgKOH/g. 2. 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 general formula (1). 4. The dispersant composition according to any one of items 1 to 3.

[In general formula (1), R ¹¹ and R ¹² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ¹¹ and R ¹² may combine with each other to form a cyclic structure. X ¹ represents a divalent linking group. ^R13 represents a hydrogen atom or a methyl group. ] 5. The dispersant composition of claim 4, wherein the block copolymer has a molecular weight distribution (PDI) of 2.5 or less. 6. The dispersant composition according to claim 4, wherein the block copolymer is polymerized by living radical polymerization. The dispersant composition according to any one of claims 1 to 6, further comprising a phenolic antioxidant. The dispersant composition according to claim 7, wherein the phenolic antioxidant is a compound represented by general formula (6).

[In general formula (6), R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁶² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁶³ represents a hydrocarbon group of 2 to 20 carbon atoms in which one or more carbon atoms are substituted with an ester group or ether group, or a hydrocarbon group of 1 to 20 carbon atoms. n represents a number from 1 to 6; However, the carbon atoms bonded to the benzene ring of R ⁶¹ are primary to tertiary carbon atoms. ] 9. The dispersant composition according to claim 7, 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 for color filters. A color filter comprising a colored layer formed using the colored composition according to claim 11 .