JP2023085227A - Dispersant, coloring composition, and color filter - Google Patents

Abstract

To provide a dispersant that can give a coloring composition with small viscosity when used as the dispersant of the coloring composition.SOLUTION: A dispersant consists of block copolymers having a block A and a block B, where the block A contains: a structural unit (a-1) that has an acidic group on a side chain part, in which the acidic group is derived from a vinyl monomer at a position separate by 2 atoms or more from a main chain; and a structural unit (a-2) derived from a (meth)acrylic vinyl monomer different from the structural unit (a-1), where the block B contains the structural unit (b-1) having a basic group, and the content of the structural unit (b-1) having a basic group in 100 mass% of the block A is 3 mass% or less.SELECTED DRAWING: None

Description

The present invention relates to dispersants, and more particularly to block copolymers that can be used as pigment dispersants in coloring compositions.

2. Description of the Related Art Conventionally, dyeing, printing, inkjet, 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 shape. It is cured by irradiation, followed by alkali development and post-baking.

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. Block copolymers that can be used as such dispersants have been proposed (see Patent Document 1 (paragraph 0050), Patent Document 2 (paragraph 0072), and Patent Document 3 (paragraph 0013)).

Further, in alkali development, binder resins having alkali solubility play a major role. However, in the case of a colored composition with a high concentration of pigment, the ratio of the binder resin, which is a developing component, is reduced, and the alkaline developability is lowered. Therefore, imparting alkali developability to the dispersant has been studied.

JP 2013-119568 A JP 2017-19937 A JP 2018-172530 A

In the step of applying the coloring composition, if the viscosity of the coloring composition is high, the formation efficiency of the coating film deteriorates and the thickness of the coating film tends to vary. Therefore, the coloring composition is required to have a low viscosity.

The present invention has been made in view of the above circumstances, and an object thereof is, for example, to provide a dispersant capable of giving a colored composition having a low viscosity when used as a dispersant for a colored composition.

The dispersant of the present invention, which has been able to solve the above problems, is a dispersant comprising a block copolymer having an A block and a B block, wherein the A block has an acidic group in its side chain portion. , a structural unit (a-1) derived from a vinyl monomer in which the acidic group is located two atoms or more away from the main chain, and a (meth)acrylic vinyl monomer different from the structural unit (a-1) The B block is characterized by containing a structural unit (b-1) having a basic group.

The dispersant (block copolymer) of the present invention has a high affinity with the dispersion medium because the A block contains the structural unit (a-1) and the structural unit (a-2). In addition, the dispersant (block copolymer) of the present invention has a high affinity with the colorant because the B block contains the structural unit (b-1). Therefore, when used as a dispersant for a coloring composition, a coloring composition having a low viscosity can be obtained.

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

When the dispersant of the present invention is used as a dispersant for a colored composition, a colored composition having a low viscosity is obtained.

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

<Dispersant>
(Block copolymer)
The dispersant of the present invention comprises a block copolymer having an A block and a B block, the A block having an acidic group in a side chain portion, and the acidic group being located at a distance of two atoms or more from the main chain. contains a structural unit (a-1) derived from a vinyl monomer in and a structural unit (a-2) derived from a (meth)acrylic vinyl monomer different from the structural unit (a-1), The B block contains a structural unit (b-1) having a basic group.

As used herein, "(meth)acrylic" means "at least one of acrylic and methacrylic". "(Meth)acrylate" means "at least one of acrylate and methacrylate". "(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 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. The “structural unit derived from (meth)acrylate” refers to a structural unit in which the radically polymerizable carbon-carbon double bond of (meth)acrylate is polymerized to form a carbon-carbon single bond.

(A block)
A block has an acidic group in the side chain portion, a structural unit (a-1) derived from a vinyl monomer in which the acidic group is located two or more atoms away from the main chain, and the structural unit (a-1 ) and a structural unit (a-2) derived from a (meth)acrylic vinyl monomer different from (a-2). By having these structural units (a-1) and structural units (a-2), it has a high affinity with the dispersion medium.

(Structural unit (a-1))
The structural unit (a-1) is a structural unit derived from a vinyl monomer having an acidic group in a side chain portion and having the acidic group separated from the main chain by two atoms or more. The structural unit (a-1) may be of only one type, or may be of two or more types.

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 phosphine group (--PO ₂ H ₂ ) and the like. Among these, the acidic group is preferably at least one selected from the group consisting of a carboxy group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group and a phosphinic acid group, from the viewpoint of moderate affinity to an alkaline developer. and a carboxy group is more preferred.

In the structural unit (a-1), the acidic group is introduced into the side chain portion, and the position thereof is separated from the main chain by two atoms or more. In the present invention, the fact that the acid group is at a position away from the main chain by two atoms or more means that the position of the carbon atom on the main chain of the polymer to which the side chain is bonded is 0 (zero), and the side chain is located from that position. It means that there is an acid group at the position after the second atom of . Atoms on the side chain may be non-carbon atoms or substituents. Specifically, for example, in the case of the following formula (X1), the acidic group X in the formula is located two atoms away from the main chain. In the following formula (X2), the acidic group X in the formula is located 5 atoms away from the main chain. In formula (X3), the acid group X is located 7 atoms away from the main chain.

In the structural unit (a-1), the acidic group is preferably located at a distance of 5 atoms or more from the main chain, and preferably at a distance of 6 atoms or more from the main chain, from the viewpoint of affinity with the dispersion medium. more preferred. In addition, from the viewpoint of solubility in an alkaline developer, the acidic group is preferably located at a distance of 18 atoms or less from the main chain, more preferably at a distance of 16 atoms or less, and preferably at a distance of 14 atoms or less from the main chain. It is even more preferred to be in position.

The structural unit (a-1) is a structural unit derived from a (meth)acrylic vinyl monomer having an acidic group in a side chain portion and having the acidic group at a position separated from the main chain by two atoms or more. is preferred, and the structural unit represented by formula (1) is more preferred from the viewpoint of viscosity.

［式（１）において、ｎ１は０または１を表す。Ｘはカルボキシ基、スルホン酸基、リン酸基、ホスホン酸基、またはホスフィン酸基を表す。Ｒ¹¹は２価の炭化水素基を表す。Ｒ¹²は２価の炭化水素基を表す。Ｒ¹³は水素原子またはメチル基を表す。］

[In formula (1), n1 represents 0 or 1. X represents a carboxy group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, or a phosphinic acid group. R ¹¹ represents a divalent hydrocarbon group. R ¹² represents a divalent hydrocarbon group. ^R13 represents a hydrogen atom or a methyl group. ]

The divalent hydrocarbon group represented by R ¹¹ and R ¹² in the formula (1) includes a divalent saturated hydrocarbon group or a divalent unsaturated hydrocarbon group. The hydrocarbon group may be linear, branched or cyclic. Specific examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group, a cycloalkylene group and an arylene group.
Examples of the alkylene group include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group and 1-methylethylene group. .
Examples of the alkenylene group include vinylene group, propenylene group, isopropenylene group, butenylene group, pentenylene group, and hexenylene group.
Examples of the cycloalkylene group include cyclobutane-1,2-diyl, cyclopentane-1,2-diyl, cyclohexane-1,2-diyl, norbornylene and adamantylene groups.
The arylene group includes a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a naphthylene group and the like.

R ¹¹ is preferably an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or an arylene group having 4 to 12 carbon atoms. An alkylene group having 1 to 12 carbon atoms and a cycloalkylene group having 3 to 12 carbon atoms are more preferable.

R ¹² is preferably an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 4 to 12 carbon atoms, and 1 carbon atom. Alkylene groups of up to 12 are more preferred.

The structural unit (a-1) is more preferably a structural unit represented by formula (11).

［式（１１）において、Ｒ¹⁴およびＲ¹⁵は、同一または異なって、水素原子、アルキル基またはアルケニル基を表す。Ｒ¹⁴およびＲ¹⁵は互いに結合して環構造を形成してもよい。Ｒ¹⁶は２価の炭化水素基を表す。Ｒ¹⁷は水素原子またはメチル基を表す。Ｙは単結合または二重結合を表す。］

[In formula (11), R ¹⁴ and R ¹⁵ are the same or different and represent a hydrogen atom, an alkyl group or an alkenyl group. R ¹⁴ and R ¹⁵ may combine with each other to form a ring structure. R ¹⁶ represents a divalent hydrocarbon group. ^R17 represents a hydrogen atom or a methyl group. Y represents a single bond or a double bond. ]

The alkyl group represented by R ¹⁴ and R ¹⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and even more preferably 1 to 4 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.

The alkenyl group represented by R ¹⁴ and R ¹⁵ preferably has 2 to 10 carbon atoms, more preferably 2 to 7 carbon atoms, and still more preferably 2 to 4 carbon atoms. Examples of the alkyl group include vinyl group, propenyl group, butenyl group, and pentenyl group.

R ¹⁴ and R ¹⁵ may combine with each other to form a ring structure. The cyclic structure formed by combining R ¹⁴ and R ¹⁵ includes a 5- to 7-membered ring structure. This ring structure may be either a non-aromatic ring or an aromatic ring, but is preferably a non-aromatic ring from the viewpoint of solubility in an alkaline developer.

The total number of carbon atoms of R ¹⁴ and R ¹⁵ is preferably 10 or less, more preferably 7 or less, and even more preferably 5 or less. At least one of R ¹⁴ and R ¹⁵ is preferably a hydrogen atom, more preferably both are hydrogen atoms.

Examples of monomers constituting the structural unit represented by formula (1) include 2-acryloyloxyethyl hydrogen succinate, 2-methacryloyloxyethyl hydrogen succinate, 2-(acryloyloxy)ethyl hydrogen hexahydrophthalate, hexa Hydrogen 2-(methacryloyloxyethyl) phthalate, 2-acryloyloxyethyl hydrogen phthalate, 2-methacryloyloxyethyl hydrogen phthalate, caprolactone 1 mol adduct of acrylic acid, caprolactone 1 mol adduct of methacrylic acid, caprolactone of acrylic acid 2 mol adducts, 2 mol caprolactone adducts of methacrylic acid, and the like.

The content of the structural unit (a-1) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more in 100% by mass of the A block, and 40% by mass or less. It is preferably 30% by mass or less, more preferably 20% by mass or less. When the content of the structural unit (a-1) is 1% by mass or more, the solubility in an alkaline developer is excellent, and when it is 40% by mass or less, the affinity between the binder resin and the dispersion medium is balanced.

(Structural unit (a-2))
The A block contains a structural unit (a-2) derived from a (meth)acrylic vinyl monomer different from the structural unit (a-1). The structural unit (a-2) may be of one kind or may be of two or more kinds.

Examples of the (meth)acrylic vinyl monomer include (meth)acrylates having a chain alkyl group, (meth)acrylates having a cyclic alkyl group, (meth)acrylates having an aromatic group, and (meth)acrylates having a hydroxy group. 1 selected from the group consisting of (meth)acrylates having an alkoxy group, (meth)acrylates having a cyclic ether group, (meth)acrylates having a polyalkylene glycol structural unit, and (meth)acrylates having a lactone-modified hydroxy group One or more vinyl monomers are included.

Examples of (meth)acrylates having a chain alkyl group include (meth)acrylates having a linear alkyl group and (meth)acrylates having a branched alkyl group.

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 preferable, and a (meth)acrylate having a linear alkyl group having 1 to 5 carbon atoms in the linear alkyl group is even more preferable. 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-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, 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 3 to 20 carbon atoms in the branched chain alkyl group, and the branched chain alkyl group having 3 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. The cyclic alkyl group includes a cyclic alkyl group having a monocyclic structure (eg, cycloalkyl group) and a cyclic alkyl group having a bridged ring structure (eg, adamantyl group, norbornyl group, isobornyl group). 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.

Specific examples of (meth)acrylates having a cyclic alkyl group having a bridged ring 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 in the aromatic group, and an aromatic group having 6 to 9 carbon atoms. A (meth)acrylate having an aromatic group is more preferred. 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.

The (meth)acrylate having a hydroxy group is preferably a hydroxyalkyl (meth)acrylate. The number of carbon atoms in the hydroxyalkyl group of the hydroxyalkyl (meth)acrylate is preferably 1-10, more preferably 1-5. The hydroxyalkyl group may be linear or branched, and preferably has one hydroxy group. Specific examples of (meth)acrylates having a hydroxy group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 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 having 1 to 5 carbon atoms are more preferred.

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

Examples of (meth)acrylates having a cyclic ether group include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrahydrofuranylmethoxyethyl (meth)acrylate, tetrahydrofuranylmethoxypropyl (meth)acrylate, tetrahydrofuranylmethoxyisopropyl (meth)acrylate. ) 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, (1,3-dioxolan-4-yl)methyl (meth)acrylate, etc. is mentioned.

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) (meth) acrylate having a polyethylene glycol structural unit such as propyl 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), and (meth)acrylates having a polypropylene glycol structural unit such as propyl ether (meth)acrylate.

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. As a structure derived from a (meth)acrylate having a lactone-modified hydroxy group, a structure represented by formula (2) is preferable.

［式（２）において、ｍは１～１０の整数である。Ｒ²¹は水素原子またはメチル基である。Ｒ²²は炭素数が１～１０のアルキレン基である。Ｒ²³は炭素数が１～１０のアルキレン基である。］

[In Formula (2), m is an integer of 1 to 10. ^R21 is a hydrogen atom or a methyl group. R ²² is an alkylene group having 1 to 10 carbon atoms. R ²³ is an alkylene group having 1 to 10 carbon atoms. ]

m in the formula (2) is preferably an integer of 1-7, more preferably an integer of 1-5.
R ²² is preferably an alkylene group having 1 to 5 carbon atoms.
R ²³ is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 3 to 8 carbon atoms.

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. .

The content of the structural unit (a-2) in the A block is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more in 100% by mass of the A block, It is preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less. When the content of the structural unit (a-2) is within the above range, the affinity between the binder resin and the dispersion medium is balanced.

The A block preferably has, as the structural unit (a-2), a structural unit (a-21) derived from a (meth)acrylate having a lactone-modified hydroxy group. In this case, the content of the structural unit (a-21) is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more in 100% by mass of the A block. % by mass or less is preferable, more preferably 80% by mass or less, and even more preferably 70% by mass or less. When the content of the structural unit (a-21) is 30% by mass or more, the solubility in an alkaline developer is improved, and when it is 90% by mass or less, the affinity between the binder resin and the dispersion medium is balanced. .

In this case, the mass ratio (a-21/a-1) between the structural unit (a-1) and the structural unit (a-21) is preferably 1 or more, more preferably 3 or more, and still more preferably It is 5 or more, preferably 30 or less, more preferably 20 or less, still more preferably 10 or less. When the mass ratio (a-21/a-1) is 1 or more, the affinity between the binder resin and the dispersion medium is balanced, and when it is 30 or less, the affinity with the dispersion medium is improved. That is, an increase in viscosity of the coloring composition can be suppressed.

The A block, as the structural unit (a-2), from the group consisting of (meth)acrylates having a chain alkyl group, (meth)acrylates having a cyclic alkyl group, and (meth)acrylates having an aromatic group It preferably has structural units (a-22) derived from one or more selected vinyl monomers. In this case, the content of the structural unit (a-22) is preferably 9% by mass or more, more preferably 17% by mass or more, and still more preferably 25% by mass or more in 100% by mass of the A block. % by mass or less is preferable, more preferably 57% by mass or less, and even more preferably 49% by mass or less. When the content of the structural unit (a-22) is within the above range, the affinity between the binder resin and the dispersion medium is well balanced, and an increase in the viscosity of the coloring composition can be suppressed.

The A block may contain only the structural unit represented by formula (a-1) and the structural unit represented by formula (a-2), or may contain other structural units. The total content of the structural unit represented by formula (a-1) and the structural unit represented by formula (a-2) in block A is preferably 70% by mass or more, more preferably 80% by mass or more. , more preferably 90% by mass or more.

The A block preferably does not substantially contain a structural unit having a basic group, which will be described later. That is, the content of the structural unit having a basic group is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.1% by mass or less in 100% by mass of the A block. and it is particularly preferable not to contain a structural unit having a basic group.
The A block preferably does not substantially contain a structural unit having a basic group forming a salt, which will be described later. That is, the content of the structural unit having a basic group forming a salt is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 100% by mass of the A block. It is particularly preferable that the content is 0.1% by mass or less and does not contain a structural unit having a basic group forming a salt.

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 contains a structural unit (b-1) having a basic group. By having the structural unit (b-1) having a basic group, it has a high affinity with the coloring material. The structural unit (b-1) may be of one kind or may be of two or more kinds.

(Structural unit having a basic group)
The structural unit having a basic group may be a structural unit derived from a vinyl monomer having a basic group. The basic group is preferably an amino group in terms of raw material availability and ease of synthesis. In the present specification, the amino group refers to a general amino group structure (—NH ₂ ), as well as —NHR ³¹ , —NR ³¹ R ³² (R ³¹ and R ³² are Each independently represents a chain or cyclic hydrocarbon group.In addition, R ³¹ and R ³² may combine with each other to form a cyclic structure.) and a substituted amino group represented by and a nitrogen-containing hetero A cyclic group (pyridyl group, imidazole group, etc.) and the like are included.

Structural unit (b-1) having a basic group is preferably a structural unit represented by formula (3).

［式（３）において、Ｒ³¹およびＲ³²は、それぞれ独立して、置換基を有していてもよい鎖状または環状の炭化水素基を表す。Ｒ³¹およびＲ³²が互いに結合して環状構造を形成していてもよい。Ｒ³³は２価の炭化水素基を表す。Ｚ³はＯまたはＮＨを表す。Ｒ³⁴は水素原子またはメチル基を表す。］

[In Formula (3), R ³¹ and R ³² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ³¹ and R ³² may combine with each other to form a cyclic structure. R ³³ represents a divalent hydrocarbon group. ^Z3 represents O or NH. ^R34 represents a hydrogen atom or a methyl group. ]

Examples of the chain hydrocarbon groups represented by R ³¹ and R ³² include straight-chain alkyl groups and branched-chain alkyl groups. The straight-chain 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. Linear alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group and the like. 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 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 ³¹ and R ³² include halogen groups, alkoxy groups, benzoyl groups (--COC ₆ H ₅ ), and hydroxy groups.

The cyclic hydrocarbon groups represented by R ³¹ and R ³² 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. Cyclic alkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. The number of carbon atoms in the aromatic group is preferably 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 phenyl group, tolyl group, xylyl group and 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 ³¹ and R ³² include halogen groups, alkoxy groups, chain alkyl groups, and hydroxy groups.

Examples of the cyclic structure formed by combining R ³¹ or R ³² 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 (3-1), (3-2), and (3-3).

［式（３－１）、（３－２）、（３－３）において、Ｒ³⁵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Ｒ³⁵は、それぞれ同一でも異なっていてもよい。］

[In formulas (3-1), (3-2) and (3-3), R ³⁵ 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 ³⁵ may be the same or different. ]

The divalent hydrocarbon group represented by R ³³ includes an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, an arenediyl group having 6 to 10 carbon atoms, and the like. Among these, an alkylene group having 1 to 10 carbon atoms is preferred. The alkylene group may be linear or branched, but preferably linear. The number of carbon atoms in the alkylene group is more preferably 1-4. Examples of the alkylene group include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group and heptamethylene group.

Specific examples of the vinyl monomer forming the structural unit represented by formula (3) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, and diethylaminoethyl (meth)acrylate. Acrylates, diethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, ethylaminoethyl (meth)acrylate, ethylaminopropyl (meth)acrylate, ethylaminobutyl (meth)acrylate, propylaminoethyl (meth)acrylate, propylamino Propyl (meth)acrylate, propylaminobutyl (meth)acrylate, dimethylaminopropyl (meth)acrylamide and the like.

The content of the structural unit having a basic group is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more in 100% by mass of the B block, and 100% by mass or less. It is preferably 99% by mass or less, more preferably 95% by mass or less. If the content of the structural unit having a basic group is within the above range, strong adsorption to the surface of the coloring material can be maintained, and an increase in viscosity of the coloring composition can be suppressed.

The B block may contain a structural unit (b-2) having a basic group forming a salt. The structural unit (b-2) having a basic group forming the salt can be formed by forming a salt with the basic group of the structural unit (b-1) having a basic group. Salts of basic groups include halide salts of basic groups (F, Cl, Br, I, etc.), inorganic salts such as sulfates; sulfonates, sulfates, phosphates or carboxylates of organic compounds. etc. As the salt of the basic group, the salt of the amino group is preferable from the viewpoint of raw material availability and ease of synthesis. In the present specification, salts of amino groups also include salts (eg, halides, etc.) of quaternary ammonium groups (--NH ₄ ⁺ , --NR ₄ ⁺ etc.).

When the B block contains the structural unit (b-2), the total content of the structural unit (b-1) and the structural unit (b-2) in the B block is 100% by mass of the B block It is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, and preferably 100% by mass or less, more preferably 99% by mass or less, further preferably 95% by mass or less.

Specific examples of the vinyl monomer that can form the other structural unit of the B block are the same as the specific examples of the monomer that can form the other structural unit of the A block.

The content of the structural unit (a-1) in the B block is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less, and contains the structural unit (a-1). It is especially preferred not to.

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 a group consisting of (AB) _m type, (AB) _m -A type and (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, from the viewpoint of handling during processing and physical properties of the composition, AB type diblock copolymer, ABA type triblock copolymer, BAB type triblock copolymer It is preferably coalesced. By forming an AB type diblock copolymer, an ABA type triblock copolymer, or a BAB type triblock copolymer, the structural unit (a-1) and It is believed that the structural unit (a-2) and the structural unit (b-1) are localized in the B block, and can efficiently act favorably with the colorant and dispersion medium (solvent). The block copolymer may have blocks other than the A block and the B block.

The content of the A block is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and preferably 99% by mass or less, based on 100% by mass of the entire block copolymer. More preferably 95% by mass or less, still more preferably 90% by mass or less. The content of the B block is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 50% by mass or less, based on 100% by mass of the entire block copolymer. It is more preferably 40% by mass or less, still more preferably 30% 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 60/40 or more, still more preferably 70/30 or more, and 99 /1 or less, more preferably 95/5 or less, and still more preferably 90/10 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 is an ABA type triblock copolymer, the mass ratio between the 1st A block and the 2nd A block (1st A block/2nd A block) is preferably 33/67 or more. , more preferably 40/60 or more, more preferably 45/55 or more, preferably 67/33 or less, more preferably 60/40 or less, still more preferably 55/45 or less. If the mass ratio (1st A block/2nd A block) is within the above range, excellent dispersibility when used as a dispersant.

The content of the structural unit (a-1) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 2.5% by mass or more in 100% by mass of the entire block copolymer. , preferably 40% by mass or less, more preferably 25% by mass or less, and even more preferably 15% by mass or less.

The content of the structural unit (a-21) is preferably 10% by mass or more, more preferably 25% by mass or more, still more preferably 35% by mass or more, based on 100% by mass of the entire block copolymer. % by mass or less is preferable, more preferably 75% by mass or less, and even more preferably 65% by mass or less.

The content of the structural unit (b-1) having a basic group is preferably 0.5% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass in 100% by mass of the entire block copolymer. % or more, preferably 50% by mass or less, more preferably 35% by mass or less, and even more preferably 25% by mass or less.

When the block copolymer contains a structural unit (b-2) having a basic group forming a salt, the content of the structural unit (b-2) is 100% by mass of the entire block copolymer. , preferably 0.5% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, preferably 50% by mass or less, more preferably 35% by mass or less, further preferably 25% by mass. It is below.

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 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, and preferably 40,000 or less, more preferably 30,000 or more. 000 or less, more preferably 20,000 or less. If Mw is within the above range, the dispersing performance when used as a dispersing agent will be better.

The molecular weight distribution of the block copolymer is preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.8 or less. In the present specification, the molecular weight distribution is determined by (weight average molecular weight (Mw) of block copolymer)/(number average molecular weight (Mn) of block copolymer). The smaller the value, the narrower the width of the molecular weight distribution, the copolymer having a uniform molecular weight. When the value is 1.0, the width of the molecular weight distribution is the narrowest. That is, the lower limit of the molecular weight distribution is 1.0. When the molecular weight distribution of the block copolymer exceeds 2.5, it includes those with small molecular weights and those with large molecular weights.

The acid value of the block copolymer is preferably 10 mgKOH/g or more, more preferably 13 mgKOH/g or more, still more preferably 15 mgKOH/g or more, preferably 100 mgKOH/g or less, more preferably 50 mgKOH/g or less, and further Preferably, it is 30 mgKOH/g or less. When the acid value is 10 mgKOH/g or more, the solubility in an alkaline developer is excellent, and when the acid value is 100 mgKOH/g or less, the affinity between the binder resin and the dispersion medium is balanced.

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, preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and further Preferably, it is 100 mgKOH/g or less. When the amine value is 10 mgKOH/g or more, the dispersibility in the coloring material is further improved, and when it is 150 mgKOH/g or less, the viscosity increase of the coloring composition can be suppressed. Further, by making the amine value of the block copolymer larger than the acid value of the block copolymer, the affinity balance between the dispersion medium and the binder resin can be adjusted to suppress the viscosity increase of the coloring composition. can.

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

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. The living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method. It is preferable in terms of precise control of distribution and easy production of a polymer with a uniform composition.

Living radical polymerization methods include methods using compounds that can generate nitroxide radicals (nitrooxide method; NMP method); A method of living polymerization from the polymerization initiation compound (ATRP method); a method of using a dithiocarboxylic acid ester or a xanthate compound (RAFT method); a method of using an organic tellurium compound (TERP method); A method using an organic iodine compound (ITP method); a method using an iodine compound as a polymerization initiator compound and an organic compound such as a phosphorus compound, a nitrogen compound, an oxygen compound, or a hydrocarbon as a catalyst (reversible transfer catalyst polymerization; RTCP method, reversible catalyst-mediated polymerization; RCMP method). Among these methods, it is preferable to use the TERP method from the viewpoint of diversity of monomers that can be used, 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 method of polymerizing a vinyl monomer using an organotellurium compound represented by general formula (6).
(b) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by general formula (6) and an azo polymerization initiator.
(c) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by general formula (6) and an organic ditelluride compound represented by general formula (7).
(d) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by general formula (6), an azo polymerization initiator, and an organic ditelluride compound represented by general formula (7).

［式（６）において、Ｒ⁶¹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。Ｒ⁶²およびＲ⁶³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。Ｒ⁶⁴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。
式（７）において、Ｒ⁶¹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 formula (6), R ⁶¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. R ⁶² and R ⁶³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁶⁴ 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 formula (7), R ⁶¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. ]

The organic tellurium compound represented by the general formula (6) is specifically ethyl = 2-methyl-2-n-butyltheranyl-propionate, ethyl = 2-n-butyltheranyl-propionate, (2-hydroxyethyl) = 2 -methyl-methylteranyl-propionate, etc., including organotellurium compounds described in WO 2004/14848, WO 2004/14962, WO 2004/072126, and WO 2004/096870 . Specific examples of the organic ditelluride compound represented by formula (7) include dimethyl ditelluride, dibutyl ditelluride, and the like. The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization. ,2′-azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis(1-cyclohexanecarbonitrile) (ACHN), 2,2′-azobis(4-methoxy-2,4- dimethylvaleronitrile) (V-70) and the like.

The polymerization step is carried out in a vessel purged with an inert gas, with a vinyl monomer and an organotellurium compound of general formula (6) for the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution, etc., according to the type of the vinyl monomer, and further adding an azo A system polymerization initiator and/or an organic ditelluride compound of general formula (7) 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.

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 include, for example, anisole, benzene, toluene, propylene glycol monomethyl ether acetate, ethyl acetate, tetrahydrofuran (THF), and the like. Examples of protic solvents include water, methanol, 1-methoxy-2-propanol and the like. A solvent may be used individually and may use 2 or more types together. The amount of the solvent to be used may be appropriately adjusted, and is preferably 0.01 ml to 50 ml per 1 g of the vinyl monomer. 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. 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 ⁶¹ (wherein R ⁶¹ 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 a radical reduction method; a method of adsorption with activated carbon or the like; a method of adsorbing a metal with an ion exchange resin or the like; these methods can also be used in combination. The other end of the copolymer obtained by the polymerization reaction (the end opposite to the growing end) is -CR ⁶² R ⁶³ R ⁶⁴ derived from a tellurium compound (wherein R ⁶² , R ⁶³ and R ⁶⁴ are represented by the formula The same as R ⁶² , R ⁶³ and R ⁶⁴ in (6)).

When quaternizing a tertiary amine group of a structural unit having a basic group, quaternizing agents include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide; aralkyl halides such as benzyl and benzyl iodide; diaryl sulfates such as diphenyl sulfate; dialkyl sulfates such as dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate; methyl p-toluenesulfonate and ethyl p-toluenesulfonate; aromatic alkyl sulfonate and the like. 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.

As a method for quaternizing a part of the tertiary amine structure of the structural unit having a basic group in the polymer, there is a method of contacting the polymer with a quaternizing agent. Specifically, there is a method of polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit having a basic group, then adding a quaternizing agent to the reaction solution and stirring. The temperature of the reaction solution to which the quaternizing agent is added is preferably 55° C. to 65° C., and the stirring time is preferably 5 hours to 20 hours.

The dispersing agent of the present invention has high dispersing performance of coloring materials and can be suitably used as a dispersing agent for coloring compositions for color filters.
In addition, the dispersant of the present invention can be used for inkjet inks, printing inks, writing utensil inks, paints, etc., because of its high dispersibility of colorants. By appropriately changing the composition of the block copolymer, it can be used not only for coloring compositions using an organic solvent but also for coloring compositions using an aqueous solvent.

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

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

(colorant)
The type and particle size of the coloring material may be appropriately selected depending on the application, and are not particularly limited. 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 multiple types.

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, 168, 177, 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, 32, 50 and the like are included. Among these pigments, C.I. I. Pigment Red 177, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 291, 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, C.I. I. Pigment Green 62, Pigment Green 63 and the like are preferred.

Further, 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 form an ionic bond with the basic group in the block copolymer contained in the dispersant and adsorb it. This dye derivative is obtained by introducing an acidic group 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 coloring material 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.

(binder resin)
The coloring composition contains a binder resin (excluding the block copolymer). Examples of the binder resin include alkali-soluble resins and polymerizable compounds (polymerizable resins, monomers having one polymerizable unsaturated bond in the molecule, monomers having two or more polymerizable unsaturated bonds in the molecule, oligomers, etc.). , thermosetting resins, and thermoplastic resins. These can be used singly or in combination of two or more. Among these, alkali-soluble resins and/or polymerizable compounds are preferred.

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

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

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

As the alkali-soluble resin, 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, and an epoxy resin into which a (meth)acrylic group has been introduced. Synthetic resins and random copolymers containing structural units derived from a carboxy group-containing vinyl monomer and structural units derived from (meth)acrylate are preferred. As the carboxy group-containing vinyl monomer, (meth)acrylic acid is preferable. Examples of the (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and cyclohexyl (meth)acrylate. , isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, 2-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 alkali-soluble resin, the total content of the structural unit derived from the carboxy group-containing vinyl monomer and the structural unit derived from (meth)acrylate is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably. is 70% by mass or more. In the alkali-soluble 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. The following is preferable, and more preferably 70% by mass or less.

Among the alkali-soluble resins, 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 alkali-soluble resin and the colorant, the alkali-soluble 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. Although the polymerization method of these random copolymers is not particularly limited, living radical polymerization is preferred from the viewpoint of alkali solubility.

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

The Mw of the alkali-soluble 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 alkali-soluble resin is 3,000 or more, the colored layer formed from the coloring composition has good heat resistance, film strength, and the like. properties are even better.

The acid value of the alkali-soluble 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 alkali-soluble 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 number of alkali-soluble resins contained in the coloring composition may be one or more. In the coloring composition, the content of the alkali-soluble resin is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass, with respect to 100 parts by mass of the coloring material, and 20 parts by mass to 80 parts by mass. is more preferred.

(Polymerizable compound)
A polymerizable resin as the polymerizable compound (for example, a linear polymer having a reactive substituent such as a hydroxy group, a carboxyl group, an amino group, etc. via an isocyanate group, an aldehyde group, an epoxy group, etc., (meth) Acrylic compounds, resins with crosslinkable groups such as cinnamic acid), compounds having one polymerizable unsaturated bond in the molecule (e.g., monofunctional (meth) acrylic monomers (alkyl (meth) acrylate, aralkyl (meth) acrylates, etc.)), compounds having two or more polymerizable unsaturated bonds in the molecule (e.g., polyfunctional (meth)acrylic monomers (di(meth)acrylates of dihydric alcohols, poly( meth) acrylate, etc.)) and the like. Polymerizable unsaturated bonds include carbon-carbon double bonds and carbon-carbon triple bonds. These can be used singly or in combination of two or more. Among these, compounds having two or more polymerizable unsaturated bonds in the molecule are preferred.

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

The content of the polymerizable compound in the coloring composition is preferably 10 parts by mass to 1,000 parts by mass, more 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 polymerizable compound is within the above range, sufficient curability will be obtained and alkali developability will also be good. It is also preferable to use an alkali-soluble resin and a polymerizable compound in combination as the binder resin.

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

(dispersion medium)
The dispersion medium used in the present invention can be appropriately selected as long as it disperses or dissolves other components constituting the coloring composition, does not react with these components, and has moderate volatility. Available. For example, conventionally known organic solvents can be used, 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 mono Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, di Glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene 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, Glycol alkyl ethers such as diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate Acetates; glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate and 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; Ethers such as propyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone , ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethylpentanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene Monohydric or polyhydric alcohols such as glycol, triethylene glycol, methoxypropanol, methoxymethylpentanol, glycerin, benzyl alcohol; n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane 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 Chains such as benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, gamma-butyrolactone, etc. 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 organic solvent is preferably glycol alkyl ether acetates, glycol monoalkyl ethers, monohydric or polyhydric alcohols, from the viewpoint of dispersibility of coloring materials and the like, solubility of dispersants, applicability of coloring compositions, and the like. Only one kind of solvent may be contained in the coloring composition, or plural kinds thereof may be used.

The dispersant of the present invention has excellent developability (KOH solubility) by introducing the structural unit (a-1) having an acidic group. In the structural unit (a-1), the acidic group is arranged at a position separated from the main chain by two atoms or more. Therefore, the dispersant of the present invention has improved compatibility particularly with glycol alkyl ether acetates.

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. It is also preferable to use a dispersion medium having a boiling point of 150° C. or higher. By using a dispersing medium having a high boiling point together, it is possible to suppress the destruction of the interrelationship of the coloring composition due to rapid drying of the coloring composition. The dispersion medium having a boiling point of 150° C. or higher may be glycol alkyl ether acetates.

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.

(Photoinitiator)
The coloring composition of the present invention may contain a photopolymerization initiator, if necessary. 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 a polymerizable compound 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, more preferably 1 to 100 parts by mass, relative to 100 parts by mass of the polymerizable compound. In this case, if the content of the photopolymerization initiator is too low, curing by exposure may be insufficient.

(Other compounding agents)
In addition to the above ingredients, other ingredients can be added to the coloring composition of the present invention as long as they do not impair the preferred physical properties of the present invention. Other compounding agents include dispersants other than the above block copolymers (urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester system dispersants, aliphatic modified polyester dispersants, etc.), sensitizing dyes, thermal polymerization inhibitors, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants ), plasticizer, organic carboxylic acid compound, organic carboxylic acid anhydride, antioxidant, ultraviolet absorber, light stabilizer, pH adjuster, preservative, antifungal agent, anticoagulant, adhesion improver, development improvement agents, storage stabilizers, and the like.

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. is 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 phosphates, 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.

Examples of organic carboxylic acid compounds include aliphatic 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, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid; aliphatic tricarboxylic acids such as tricarballylic acid and aconitic acid; benzoic acid , phthalic acid, trimesic acid, pyropetic acid, merophanic acid, and other aromatic carboxylic acids in which a carboxyl group is directly bonded to a phenyl group; and aromatic carboxylic acids in which a carboxyl group is bonded via a carbon bond. By containing an organic carboxylic acid compound, alkali developability and scumming can be improved.

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. By containing an organic carboxylic acid anhydride, alkali developability and scumming can be improved.

<Method for producing colored composition>
The coloring composition can be prepared by mixing a coloring agent, a dispersant (or a dispersant solution), a binder resin, a dispersion medium, and, if necessary, a photopolymerization initiator and other ingredients. For mixing, for example, a mixing and dispersing machine such as a paint shaker, bead mill, ball mill, dissolver or kneader can be used. The coloring composition is preferably filtered after mixing. Since the coloring composition has alkali developability, it can be suitably used for a color filter. As an alkaline developer, an aqueous solution containing an organic solvent or a surfactant and an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide, or the like can be used.

<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. First, thermoplastic resin sheets such as polyester resins, polyolefin resins, polycarbonate resins and polymethyl methacrylate resins, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins and poly(meth)acrylic resins, various types of glass After applying a coloring composition in which a red pigment is dispersed, for example, on a transparent substrate such as the above, pre-baking is performed to evaporate the solvent (dispersion medium) to form a coating film. Next, after exposing this coating film through a photomask, an alkaline developer (an organic solvent or an aqueous solution containing a surfactant and an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide, etc. etc.) to dissolve and remove the unexposed areas of the coating film. 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 a green coloring composition or a blue coloring composition, each coloring composition is applied, pre-baked, exposed, developed and post-baked in the same manner as described above to obtain a green pixel array and a blue pixel array. are sequentially formed on the same substrate. 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. A black matrix may be provided on the transparent substrate used for forming the three primary color pixel arrays of red, green and blue.

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

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

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

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 (Mw/Mn), amine value and acid value of the dispersant and binder resin, and the viscosity, particle size, KOH solubility and TMAH solubility of the coloring composition are , was evaluated according to the following method.

Abbreviations have the following meanings.
BTEE: ethyl = 2-methyl-2-n-butyltheranyl-propionate DBDT: dibutyl ditelluride AIBN: 2,2'-azobis(isobutyronitrile)
BMA: n-butyl methacrylate CL5MA: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (manufactured by Daicel Chemical, Plaxel (registered trademark) FM5)
M4EGMA: Methoxy polyethylene glycol monomethacrylate (trade name: Blemmer (registered trademark) PME-200, manufactured by NOF)
HEMA: 2-hydroxyethyl methacrylate THFMA: tetrahydrofurfuryl methacrylate (biocarbon content 56% by mass)
THFEOMA: Tetrahydrofuranyl methoxyethyl methacrylate THFPOMA: Tetrahydrofuranyl methoxy isopropyl methacrylate GLYFOMA: Glycerol formal methacrylate (biocarbon content 38% by mass)
MAA: methacrylic acid MOESA: 2-methacryloyloxyethyl hydrogen succinate MOECHDA: 2-(methacryloyloxy) ethyl hydrogen hexahydrophthalate MOEBDA: 2-methacryloyloxyethyl hydrogen phthalate CACL2A: 2 mol caprolactone adduct of acrylic acid (Toagosei made by M-5300)
DMAEMA: dimethylaminoethyl methacrylate BzMA: benzyl methacrylate BzCl: benzyl chloride PMA: propylene glycol monomethyl ether acetate MeOH: methanol TMAH: tetramethylammonium hydroxide

(Polymerization rate)
¹ H-NMR was measured (solvent: CDCl ₃ , internal standard: tetramethylsilane) using a nuclear magnetic resonance (NMR) spectrometer (manufactured by Bruker Biospin, model: AVANCE500 (frequency: 500 MHz)). For the obtained NMR spectrum, the integration ratio of the peak derived from the monomer and the peak derived from the polymer was obtained to calculate the polymerization rate of the monomer.

(Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn))
It was determined by gel permeation chromatography (GPC) using a high-performance liquid chromatograph (manufactured by Tosoh, model HLC-8320). The column is one SHODEX KF-603 (φ6 mm × 150 mm) (manufactured by SHODEX), the mobile phase is lithium bromide (10 mmol/L)-acetic acid (10 mmol/L)-methylpyrrolidone solution, and the detector is a differential refractometer. bottom. The measurement conditions were a column temperature of 40° C., a sample concentration of 10 mg/mL, a sample injection amount of 10 μm, and a flow rate of 0.2 mL/min. Polystyrene (molecular weight 70,500, 37,900, 19,920, 10,200, 4,910, 2,630, 1,150) 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 (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 hydrochloric acid (0.1 mol/L)-propanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi Chemical). Using the inflection point of the titration pH curve as the titration end point, the amine value (B) was calculated by the following equation.
B = 56.11 x Vs x 0.1 x f/w
B: amine value (mgKOH/g)
Vs: Hydrochloric acid (0.1 mol / L) required for titration - amount of propanol solution used (mL)
f: Potency of hydrochloric acid (0.1 mol/L) (propanolic) 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. Dissolve the measurement sample in tetrahydrofuran, add several drops of 1.0 w/v% phenolphthalein ethanol (90) solution to the resulting solution as an indicator, and neutralize with potassium hydroxide (0.1 mol/L)-ethanol solution. Titrated. The acid value was calculated according to the following formula, with the point where a little redness remained as the end point of the titration.
A = 56.11 x Vs x 0.1 x f/w
A: Acid value (mgKOH/g)
Vs: potassium hydroxide (0.1 mol / L) required for titration - amount of ethanol solution used (mL)
f: potassium hydroxide (0.1 mol / L) - titer of ethanol solution w: mass of measurement sample (g) (converted to solid content)

(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. In addition, the measurement was performed on the colored composition stored at 25° C. for one week after preparation.

(Particle size)
Particle size was measured at 25° C. using a concentrated particle size analyzer (trade name: FPAR-1000, manufactured by Otsuka Electronics). Samples were diluted with propylene glycol monomethyl ether acetate (PGMEA) as needed. In addition, the measurement was performed on the colored composition stored at 25° C. for one week after preparation.

(KOH solubility)
On a surface-washed glass plate (50 mm × 50 mm), a spin coater (trade name: MS-A100, manufactured by Mikasa) was used to form a coating film of the coloring composition at 500 rpm for 5 seconds. dried for a minute. Next, the glass plate on which the coating film was formed was immersed in a 0.05% potassium hydroxide aqueous solution (10 mL), allowed to stand at 25° C. for 30 minutes, and the solubility was observed.
Solubility was measured using an ultraviolet-visible spectrophotometer (product name: spectrophotometer U-3900, manufactured by Hitachi) and a quartz cell (10 × 10 × 40 mm) for an aqueous potassium hydroxide solution in which at least a portion of the coating film was dissolved. Absorbance was analyzed at a wavelength of 612 nm for the blue pigment dispersion, 551 nm for the red pigment dispersion, and 644 nm for the green pigment dispersion. A higher absorbance indicates a higher KOH solubility of the coating film.

(TMAH solubility)
On a surface-washed glass plate (50 mm × 50 mm), a spin coater (trade name: MS-A100, manufactured by Mikasa) was used to form a coating film of the coloring composition at 500 rpm for 5 seconds. dried for a minute. Next, the glass plate on which the coating film was formed was immersed in a 0.05% TMAH aqueous solution (10 mL), allowed to stand at 25° C. for 30 minutes, and the solubility was observed.
Solubility was measured using an ultraviolet-visible spectrophotometer (product name: spectrophotometer U-3900, manufactured by Hitachi) and a quartz cell (10 × 10 × 40 mm) for the TMAH aqueous solution in which at least a part of the coating film was dissolved. The absorbance was analyzed at a wavelength of 551 nm for the red pigment dispersion and 644 nm for the green pigment dispersion. The higher the absorbance, the higher the TMAH solubility of the coating film.

<Synthesis of block copolymer>
(Block copolymer No. 1)
A flask equipped with an argon gas inlet tube and a stirrer was charged with 70.4 g of BMA, 145.4 g of CL5MA, 7.8 g of MAA, 0.9 g of AIBN, and 149.0 g of PMA. 0 g was added and reacted at 60° C. for 16 hours to polymerize the A block. The polymerization rate was 99%.

To the reaction solution, a solution of 26.4 g of DMAEMA and 17.6 g of PMA, which had been replaced with argon in advance, was added and reacted at 60° C. for 22 hours to polymerize the B block. The polymerization rate was 98%.

After completion of the reaction, the reaction solution was poured into n-heptane which was being stirred. Block copolymer No. 1 was obtained by filtering the precipitated polymer with suction and drying it. got 1. Obtained block copolymer no. 1 had an Mw of 17,906, an Mw/Mn of 1.36, an acid value of 22 mgKOH/g, and an amine value of 36 mgKOH/g.

(Block copolymer Nos. 2 to 14)
Block copolymer no. Block copolymer No. 1 was prepared in the same manner as in the production method of No. 1. 2-14 were produced. Tables 1 and 2 show the monomers, organic tellurium compounds, organic ditelluride compounds, azo polymerization initiators, solvents, reaction conditions, polymerization rates, and quaternization rates used. Tables 3 and 4 show the composition, Mw, Mw/Mn, acid value and amine value of each block copolymer. The content of each structural unit in the copolymer was calculated from the charging ratio and polymerization rate of the monomers used in the polymerization reaction.

<Synthesis of alkali-soluble resin (binder resin)>
A flask equipped with an argon gas inlet tube and a stirrer was charged with 20.0 g of MAA, 80.0 g of BzMA, and 290.0 g of PMA. was added and the temperature was raised to 90°C. While maintaining the solution at 90° C., 40.0 g of MAA, 160.0 g of BzMA, 3.0 g of AIBN, 4.0 g of n-dodecanethiol, and 25.0 g of PMA were added dropwise to the solution over 1.5 hours. After 60 minutes from the completion of the dropwise addition, the temperature was raised to 110° C., 0.3 g of AIBN and 5.0 g of PMA were added and reacted for 1 hour, and further 0.3 g of AIBN and 5.0 g of PMA were added and allowed to react for 1 hour. Further, 0.3 g of AIBN and 5.0 g of PMA were added and reacted for 1 hour.

The resulting reaction solution was cooled to room temperature, 120.0 g of PMA was added, and an alkali-soluble resin solution having a nonvolatile content of 39.9% was obtained. The alkali-soluble resin had an Mw of 11,873, an Mw/Mn of 1.77, and an acid value of 127 mgKOH/g.

<Preparation of coloring composition>
(Coloring composition No. 1)
1.8 parts by weight of pigment, 1.4 parts by weight of dispersant (solution of block copolymer No. 1) (40 parts by weight of block copolymer per 100 parts by weight of pigment), 1.8 parts by weight of alkali-soluble resin solution A blending composition was prepared so that it would be 13 parts by mass of PMA (40 parts by mass of alkali-soluble resin for 100 parts by mass of pigment), 50 parts by mass of 0.3 mm zirconia beads were added, and a bead mill (trade name: DISPERMAT CA , VMA-GETZMANN GmbH) for 3 hours to fully disperse. After completion of dispersion, the beads were separated by filtration to obtain a colored composition. Pigments include C.I. I. Pigment Blue 15:6 (trade name: FASTOGEN (registered trademark) Blue A540, manufactured by DIC) was used. The resulting colored composition was evaluated for viscosity and particle size, and the results are shown in Table 5. The KOH solubility evaluation result was an absorbance of 0.066.

(Coloring composition No. 2-4)
Except for changing the dispersant (block copolymer), colored composition No. Coloring composition No. 1 was prepared in the same manner as in the preparation method of No. 1. 2-4 were prepared. The resulting colored composition was evaluated for viscosity and particle size, and the results are shown in Table 3. The evaluation result of KOH solubility is the coloring composition No. 2 has an absorbance of 1.229; The absorbance of Coloring Composition No. 3 is 0.083. The absorbance of 4 was 0.003.

(Coloring composition No. 5)
1.5 parts by weight of pigment, 2.0 parts by weight of dispersant (solution of block copolymer No. 5) (60 parts by weight of block copolymer per 100 parts by weight of pigment), 2.3 parts by weight of alkali-soluble resin solution A blending composition was prepared so that it would be 12.2 parts by mass of PMA (60 parts by mass of alkali-soluble resin for 100 parts by mass of pigment), 100 parts by mass of 0.3 mm zirconia beads were added, and a bead mill (trade name: DISPERMAT CA, manufactured by VMA-GETZMANN GmbH) for 3 hours to sufficiently disperse. After completion of dispersion, the beads were separated by filtration to obtain a colored composition. Pigments include C.I. I. Pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals) was used. The resulting colored composition was evaluated for viscosity and particle size, and the results are shown in Table 3. The KOH solubility was evaluated to have an absorbance of 1.408. The TMAH solubility evaluation result was an absorbance of 0.984.

(Coloring composition No. 6 to 13)
Except for changing the dispersant (block copolymer), colored composition No. Coloring composition No. 5 was prepared in the same manner as in the preparation method of No. 5. 6-13 were prepared. The resulting colored composition was evaluated for viscosity and particle size, and the results are shown in Table 3.
The KOH solubility evaluation results are based on the coloring composition No. The absorbance of Coloring Composition No. 6 is 1.022. The absorbance of Coloring Composition No. 7 is 0.802. The absorbance of coloring composition No. 8 is 1.696. The absorbance of 9 was 0.154. The evaluation result of TMAH solubility is the coloring composition No. The absorbance of Coloring Composition No. 6 is 0.667. The absorbance of Coloring Composition No. 7 is 0.180. The absorbance of Coloring Composition No. 8 is 0.795. The absorbance of 9 was 0.245.

(Coloring composition No. 14)
1.5 parts by mass of pigment, 1.7 parts by mass of dispersant (solution of block copolymer No. 14) (60 parts by mass of block copolymer per 100 parts by mass of pigment), 2.3 parts by mass of alkali-soluble resin solution A blending composition was prepared so as to be 12.5 parts by mass of PMA (60 parts by mass of alkali-soluble resin for 100 parts by mass of pigment), 100 parts by mass of 0.3 mm zirconia beads were added, and a bead mill (trade name: DISPERMAT CA, manufactured by VMA-GETZMANN GmbH) for 3 hours to sufficiently disperse. After completion of dispersion, the beads were separated by filtration to obtain a colored composition. Pigments include C.I. I. Pigment Green 59 (trade name: FASTOGEN (registered trademark) GREEN C100, manufactured by DIC) was used. The resulting colored composition was evaluated for viscosity and particle size, and the results are shown in Table 3. The KOH solubility evaluation result was an absorbance of 0.267. The TMAH solubility evaluation result was an absorbance of 0.302.

Coloring composition no. 1 is the case where the block copolymer contained as the dispersant does not have the structural unit (a-1). This coloring composition no. In No. 1, the dispersibility of the blue pigment was poor, the viscosity of the composition was high, and the particle size of the pigment was large.

Coloring composition no. 2 to 4, the AB type block copolymer or the ABA type triblock copolymer contained as a dispersant has an acidic group in the side chain portion in the A block, A structural unit (a-1) derived from a vinyl monomer in which the acidic group is located two atoms or more away from the main chain, and a structure derived from a (meth)acrylic vinyl monomer different from the structural unit (a-1). In this case, the B block contains a structural unit (b-1) having a basic group.
These coloring compositions no. In 2 to 4, the dispersibility of the blue pigment was good, the viscosity of the composition was low, and the particle size of the blue pigment was small.

Also, in particular, coloring composition No. 2 was also excellent in KOH solubility. Coloring composition no. 5 to 13 are red pigments, and coloring composition Nos. No. 14 is the case where a green pigment is dispersed, and it can be seen that the dispersant of the present invention has excellent dispersibility not only for a blue pigment but also for a red pigment and a green pigment. Moreover, not only KOH solubility but also TMAH solubility is good.

The present invention includes the following embodiments.
(Embodiment 1)
A dispersant comprising a block copolymer having an A block and a B block,
The structural unit (a-1) derived from a vinyl monomer in which the A block has an acidic group in a side chain portion, and the acidic group is located two atoms or more away from the main chain, and the structural unit (a- 1) containing a structural unit (a-2) derived from a (meth)acrylic vinyl monomer different from
The B block contains a structural unit (b-1) having a basic group,
A dispersant, wherein the content of the structural unit (b-1) having a basic group in 100% by mass of the A block is 3% by mass or less.

(Embodiment 2)
The dispersant according to Embodiment 1, wherein the structural unit (a-1) is a structural unit represented by formula (1).

［式（１）において、ｎ１は０または１を表す。Ｘはカルボキシ基、スルホン酸基、リン酸基、ホスホン酸基、またはホスフィン酸基を表す。Ｒ¹¹は２価の炭化水素基を表す。Ｒ¹²は２価の炭化水素基を表す。Ｒ¹³は水素原子またはメチル基を表す。］

[In formula (1), n1 represents 0 or 1. X represents a carboxy group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, or a phosphinic acid group. R ¹¹ represents a divalent hydrocarbon group. R ¹² represents a divalent hydrocarbon group. ^R13 represents a hydrogen atom or a methyl group. ]

(Embodiment 3)
3. The dispersant according to embodiment 1 or 2, wherein the block copolymer has an acid value of 10 mgKOH/g to 100 mgKOH/g.

(Embodiment 4)
4. The dispersant according to any one of embodiments 1-3, wherein the block copolymer has an amine value of from 10 mg KOH/g to 150 mg KOH/g.

(Embodiment 5)
The dispersant according to any one of Embodiments 1 to 4, wherein the structural unit (b-1) is a structural unit represented by formula (3).

［式（３）において、Ｒ³¹およびＲ³²は、それぞれ独立して、置換基を有していてもよい鎖状または環状の炭化水素基を表す。Ｒ³¹およびＲ³²が互いに結合して環状構造を形成していてもよい。Ｒ³³は２価の炭化水素基を表す。Ｚ³はＯまたはＮＨを表す。Ｒ³⁴は水素原子またはメチル基を表す。］

[In Formula (3), R ³¹ and R ³² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ³¹ and R ³² may combine with each other to form a cyclic structure. R ³³ represents a divalent hydrocarbon group. ^Z3 represents O or NH. ^R34 represents a hydrogen atom or a methyl group. ]

(Embodiment 6)
The (meth)acrylic vinyl monomer is a (meth)acrylate having a chain alkyl group, a (meth)acrylate having a cyclic alkyl group, a (meth)acrylate having an aromatic group, a (meth)acrylate having a hydroxy group, One selected from the group consisting of (meth)acrylates having an alkoxy group, (meth)acrylates having a cyclic ether group, (meth)acrylates having a polyalkylene glycol structural unit, and (meth)acrylates having a lactone-modified hydroxy group Or the dispersant according to any one of embodiments 1-5, which is two or more vinyl monomers.

(Embodiment 7)
7. The dispersant according to any one of Embodiments 1 to 6, wherein the content of the structural unit (a-2) is 60% by mass to 99% by mass in 100% by mass of the A block.

(Embodiment 8)
8. The dispersant according to any one of embodiments 1 to 7, wherein the mass ratio of A block to B block (A block/B block) in the block copolymer is from 50/50 to 99/1.

(Embodiment 9)
9. The dispersant according to any one of embodiments 1-8, wherein the block copolymer has a weight average molecular weight (Mw) of 5,000 to 40,000.

(Embodiment 10)
The dispersant according to Embodiments 1 to 9, wherein the block copolymer is obtained by living radical polymerization and has a molecular weight distribution (Mw/Mn) of 2.5 or less.

(Embodiment 11)
A coloring composition comprising the dispersant according to embodiment 1 or 2, a coloring material, a binder resin and a dispersing medium.

(Embodiment 12)
12. The colored composition according to embodiment 11, which is for color filters.

(Embodiment 13)
A color filter comprising a colored layer formed using the colored composition according to claim 11.

Claims (13)

A dispersant comprising a block copolymer having an A block and a B block,
The structural unit (a-1) derived from a vinyl monomer in which the A block has an acidic group in a side chain portion, and the acidic group is located two atoms or more away from the main chain, and the structural unit (a- 1) containing a structural unit (a-2) derived from a (meth)acrylic vinyl monomer different from
The B block contains a structural unit (b-1) having a basic group,
A dispersant, wherein the content of the structural unit (b-1) having a basic group in 100% by mass of the A block is 3% by mass or less. The dispersant according to claim 1, wherein the structural unit (a-1) is a structural unit represented by formula (1).

[In formula (1), n1 represents 0 or 1. X represents a carboxy group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, or a phosphinic acid group. R ¹¹ represents a divalent hydrocarbon group. R ¹² represents a divalent hydrocarbon group. ^R13 represents a hydrogen atom or a methyl group. ] 3. The dispersant according to claim 1, wherein the block copolymer has an acid value of 10 mgKOH/g to 100 mgKOH/g. 3. The dispersant according to claim 1, wherein the block copolymer has an amine value of 10 mgKOH/g to 150 mgKOH/g. 3. The dispersant according to claim 1, wherein the structural unit (b-1) is a structural unit represented by formula (3).

[In Formula (3), R ³¹ and R ³² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ³¹ and R ³² may combine with each other to form a cyclic structure. R ³³ represents a divalent hydrocarbon group. ^Z3 represents O or NH. ^R34 represents a hydrogen atom or a methyl group. ] The (meth)acrylic vinyl monomer is a (meth)acrylate having a chain alkyl group, a (meth)acrylate having a cyclic alkyl group, a (meth)acrylate having an aromatic group, a (meth)acrylate having a hydroxy group, One selected from the group consisting of (meth)acrylates having an alkoxy group, (meth)acrylates having a cyclic ether group, (meth)acrylates having a polyalkylene glycol structural unit, and (meth)acrylates having a lactone-modified hydroxy group or two or more vinyl monomers. 3. The dispersant according to claim 1, wherein the content of the structural unit (a-2) is 60% by mass to 99% by mass in 100% by mass of the A block. 3. The dispersant according to claim 1, wherein the block copolymer has a mass ratio of A block to B block (A block/B block) of 50/50 to 99/1. 3. The dispersant according to claim 1, wherein the block copolymer has a weight average molecular weight (Mw) of 5,000 to 40,000. 3. The dispersant according to claim 1, wherein the block copolymer is obtained by living radical polymerization and has a molecular weight distribution (Mw/Mn) of 2.5 or less. A coloring composition comprising the dispersant according to claim 1 or 2, a coloring material, a binder resin and a dispersion medium. The coloring composition according to claim 11, which is for color filters. A color filter comprising a colored layer formed using the colored composition according to claim 11 .