TWI818051B - Dispersant composition, coloring composition, and color filter - Google Patents

Abstract

An object of the present invention is to provide a dispersant composition that produces less formaldehyde over time. The solution of the present invention is a dispersant composition containing a polymer having a structure represented by the general formula (5) in the side chain. *-Y ¹ -NR ¹¹ R ¹² (5) [In the general formula (5), R ¹¹ represents a hydrogen atom and a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure. Y ¹ represents a divalent hydrocarbon group. *Indicates bonding. ]

Description

Dispersant composition, coloring composition, and color filter

The present invention relates to dispersant compositions containing polymers.

In the past, when manufacturing color filters used in liquid crystal displays and the like, known methods for imparting a coloring material to a substrate include dyeing, printing, inkjet, electroplating, and pigment dispersion. From the viewpoint of spectral characteristics, durability, pattern shape and accuracy, the mainstream of these is the pigment dispersion method. In this pigment dispersion method, a coating film composed of a colored composition mixed with a pigment, a dispersant, a dispersion medium (solvent), a binder resin, etc. is formed on a substrate, and is irradiated with radiation through a mask with a desired pattern shape to harden it. Perform alkaline development.

In recent years, in order to obtain good color reproducibility and high contrast of color filters, high concentration of pigments in coloring compositions has been reviewed. When the pigment concentration is increased, the relative proportion of the dispersant decreases, so the dispersant is required to have high dispersibility (see, for example, Patent Document 1 (paragraph 0004)). In addition, in alkaline development, alkali-soluble binder resin plays an important role. However, in the case of a pigment dispersion composition in which the pigment is highly concentrated, the proportion of the binder resin in the developing component is reduced, thereby reducing the alkaline developability. Therefore, the dispersant is also required to have alkaline developability that is originally required for the binder resin. As such a dispersant, Patent Document 2 describes the use of an A-B block copolymer as a pigment dispersant. The A-B block copolymer is composed of an A block having a polylactone chain in the side chain and a tertiary amine in the side chain. It is composed of the B block of the base (refer to Patent Document 2 (paragraphs 0023~0045)). [Previous technical document] [Patent document]

Patent Document 1: Japanese Patent Application Publication No. 2009-265515. Patent Document 2: Japanese Patent Application Publication No. 2013-119568.

[Technical problem to be solved by the invention] In resin-type dispersants, in order to improve the dispersibility of coloring materials, it is proposed to introduce a tertiary amine group into the side chain (see Patent Document 2). However, resin dispersants with tertiary amine groups will produce formaldehyde over time due to the tertiary amine groups. Therefore, if such a resin-type dispersant is used in a coloring composition, formaldehyde will be contained in the coloring composition. In recent years, environmental standards have become more stringent, so if conventional resin-based dispersants are used, the amount of formaldehyde in the coloring composition does not meet the environmental standards.

The present invention was made in view of the above-mentioned circumstances, and it is an object of the present invention to provide a dispersant composition that generates less formaldehyde over time.

[Technical means used to solve technical problems] The dispersant composition of the present invention that can solve the above problems contains a polymer having a structure represented by the general formula (5) in the side chain. *-Y1-N-R11R12 (5) [In the general formula (5), R11 represents a hydrogen atom and a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R12 represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R11 and R12 can bond with each other to form a cyclic structure. Y1 represents a divalent hydrocarbon group. *Indicates bonding. ]

If a polymer having an amine group is used as a dispersant, formaldehyde will be generated over time due to the amine group. Surprisingly, the present invention can inhibit the generation of formaldehyde over time by making the amine group have a specific structure (the structure represented by the general formula (5)), and can reduce the formaldehyde in the dispersant composition. Furthermore, excellent coloring material dispersion properties can be obtained.

The present invention includes a colored composition, which contains the aforementioned dispersant composition, coloring material, binder resin and dispersion medium. Furthermore, the present invention includes a color filter including a colored layer formed using the above-mentioned colored composition.

[Effects of the invention] According to the present invention, a dispersant composition that generates less formaldehyde over time can be obtained.

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

In the present invention, "(meth)acrylic acid group" means "at least one of acrylic acid group and methacrylic acid group". "(Meth)acrylic acid group monomer" is a monomer having a "(meth)acrylyl group" in a molecule. "(Meth)acrylyl" means "at least one of acrylyl and methacrylyl". "Vinyl monomer" is a monomer with a free radical polymerizable carbon-carbon double bond in the molecule. "Structural unit derived from a (meth)acrylic acid-based monomer" refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a (meth)acrylic acid-based monomer is polymerized to form a carbon-carbon single bond. "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.

>Dispersant composition> The dispersant composition of the present invention contains a polymer having a structure represented by the general formula (5) in the side chain. *-Y ¹ -NR ¹¹ R ¹² (5) [In the general formula (5), R ¹¹ represents a hydrogen atom and a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure. Y ¹ represents a divalent hydrocarbon group. *Indicates bonding. ]

If a polymer having an amine group is used as a dispersant, formaldehyde will be generated over time due to the amine group. Surprisingly, the present invention can inhibit the generation of formaldehyde over time by making the amine group have a specific structure (the structure represented by the general formula (5)), and can reduce the formaldehyde in the dispersant composition. Furthermore, excellent coloring material dispersion properties can be obtained.

Examples of the chain hydrocarbon group represented by R11 and R12 include a linear alkyl group, a branched alkyl group, and the like. The carbon number of the linear alkyl group is preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 2 to 5 carbon atoms. Examples of the linear alkyl group include ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-lauryl, and the like. The branched alkyl group preferably has a carbon number of 3 to 20 carbon atoms, more preferably a carbon number of 3 to 10 carbon atoms, and still more preferably a carbon number of 3 to 5 carbon atoms. Examples of the branched alkyl group include isopropyl, isobutyl, second butyl, third butyl, 2-ethylhexyl, neopentyl, isooctyl, and the like.

Examples of the substituents of the chain hydrocarbon group represented by R11 and R12 include a halo group, an alkoxy group, a benzyl group (-COC6H5), a hydroxyl group, and the like.

Examples of the cyclic hydrocarbon group represented by R11 and R12 include a cyclic alkyl group, an aromatic group, and the like, and the cyclic alkyl group and the aromatic group may have a chain portion. The carbon number of the aforementioned cyclic alkyl group is preferably 4 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms. Examples of the cyclic alkyl group include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. The aromatic group preferably has a carbon number of 6 to 18 carbon atoms, more preferably a carbon number of 6 to 12 carbon atoms, and still more preferably a carbon number of 6 to 8 carbon atoms. Examples of the aromatic group include phenyl, tolyl, styryl, mesityl, and the like. Examples of the chain part of the cyclic alkyl group having a chain part and the aromatic group having a chain part include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms. More preferably, it is an alkylene group having 1 to 3 carbon atoms.

Examples of the substituents of the cyclic hydrocarbon group represented by R ¹¹ and R ¹² include a halo group, an alkoxy group, a chain alkyl group, a hydroxyl group, and the like.

The cyclic structure formed by the mutual bonding of R ¹¹ and R ¹² can be, for example, a nitrogen-containing heterocyclic ring with 5 to 7 members or a condensed ring formed by the condensation of two of these rings. The nitrogen-containing heterocyclic ring is preferably not aromatic, and more preferably is a saturated ring.

Examples of the divalent hydrocarbon group represented by Y ¹ include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, and an aromatic hydrocarbon diyl group having 6 to 10 carbon atoms. Among these, an alkylene group having 1 to 10 carbon atoms is preferred. The aforementioned alkylene group may be either linear or branched, and is preferably linear. Y ¹ is preferably an alkylene group having 1 to 5 carbon atoms.

Examples of the -NR ¹¹ R ¹² part of the structure represented by the general formula (5) include monoalkylamino groups such as ethylamine group, propylamine group, and tert-butylamine group; diethylamine group, dipropylamine group, bis(2 -Hydroxyethyl)amine and other dialkylamino groups.

Examples of polymers having a structure represented by the general formula (5) in the side chain include (meth)acrylic polymers, polyurethane polymers, polyester polymers, polyallylamine polymers, and carbon polymers. Diimine polymers, etc.

From the viewpoint of adsorption of coloring materials and dispersion of coloring materials, the amine value of the polymer having a structure represented by the general formula (5) in the side chain is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more. , more preferably 80 mgKOH/g or more, more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, still more preferably 120 mgKOH/g or less.

The molecular weight of the polymer having the structure represented by the general formula (5) in the side chain is measured by gel permeation chromatography. The weight average molecular weight (Mw) of the aforementioned polymer is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, particularly preferably 6,000 or more, preferably 40,000 or less, more preferably 30,000 or less, still more preferably The price is below 25,000, and the best price is below 20,000. If the weight average molecular weight is within the above range, the dispersion performance when used as a dispersant will be better. The above descriptions and explanations are only descriptions of the preferred embodiments of the present invention. Those with ordinary knowledge of this technology may make other modifications based on the patent scope defined below and the above explanations, but these modifications should still be made. It is for the spirit of the present invention and within the scope of rights of the present invention.

(block copolymer) From the viewpoint of dispersibility, the polymer is preferably a block copolymer having an A block and a B block, the A block having a structural unit derived from a (meth)acrylic acid-based monomer, and the B block The block has a structural unit represented by general formula (1).

[Chemical formula 1] [In the general formula (1), R ¹¹ represents a hydrogen atom and a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure. R ¹³ represents a hydrogen atom or a methyl group. X ¹ represents a amide group, an ester group, or a single bond. Y ¹ represents a divalent hydrocarbon group. ]

Various structural components of the above-mentioned block copolymer will be described below.

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

The content rate of the structural unit derived from the (meth)acrylic acid group monomer is preferably 80 mass% or more, more preferably 90 mass% or more, and still more preferably 95 mass% in 100 mass% of the A block Above, the best value is 100% by mass.

Examples of the (meth)acrylic monomer include (meth)acrylate having a chain alkyl group (linear alkyl group or branched alkyl group), (meth)acrylate having a cyclic alkyl group, (Meth)acrylate with polycyclic structure, (meth)acrylate with aromatic group, (meth)acrylate with polyalkylene glycol structural unit, (meth)acrylate with hydroxyl group, internal Ester modified (meth)acrylate with hydroxyl group, (meth)acrylate with alkoxy group, (meth)acrylate with oxygen-containing heterocyclic group, (meth)acrylate with acidic group, (Meth)acrylic acid and the like can be used alone or in combination of two or more kinds thereof.

The aforementioned (meth)acrylate having a linear alkyl group is preferably a (meth)acrylate having a linear alkyl carbon number of 1 to 20, more preferably a linear alkyl carbon number. It is a linear alkyl (meth)acrylate of 1 to 10. Examples of the (meth)acrylate having a linear alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, decyl (meth)acrylate, n-lauryl (meth)acrylate, n-hard (meth)acrylate Fatty esters, etc.

The aforementioned (meth)acrylate having a branched chain alkyl group is preferably a (meth)acrylate having a branched chain alkyl group with a branched chain alkyl carbon number of 3 to 20, and more preferably a branched chain alkyl group having a branched chain alkyl carbon number. It is a (meth)acrylate with 3 to 10 branched chain alkyl groups. Examples of the (meth)acrylate having a branched alkyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, and third butyl (meth)acrylate. Tributyl ester, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, etc.

The (meth)acrylate having a cyclic alkyl group is preferably a (meth)acrylate having a cyclic alkyl group having a cyclic alkyl carbon number of 6 to 12. Examples of the cyclic alkyl group include a cyclic alkyl group having a monocyclic structure (for example, a cycloalkyl group). Specific examples of (meth)acrylic acid esters having a cyclic alkyl group with a monocyclic structure include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, and cyclododecyl (meth)acrylate. Alkyl esters, etc.

The (meth)acrylate having a polycyclic structure is preferably a (meth)acrylate having a polycyclic structure having a carbon number of 6 to 12. Examples of the polycyclic structure include cyclic alkyl groups having a cross-linked ring structure (for example, adamantyl, norbornyl, isobornyl). Specific examples of (meth)acrylates having a polycyclic structure include isocamphenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and dicyclopentyl (meth)acrylate. Oxyethyl ester, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, etc.

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

Examples of the aforementioned (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) 10) Ethyl ether (meth)acrylate, polyethylene glycol (degree of polymerization = 2~10) propyl ether (meth)acrylate, polyethylene glycol (degree of polymerization = 2~10) phenyl ether ( Methacrylates and other (meth)acrylates with polyethylene glycol structural units; polypropylene glycol (degree of polymerization = 2~10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization = 2~10 ) Ethyl ether (meth)acrylate, polypropylene glycol (degree of polymerization = 2~10) propyl ether (meth)acrylate, polypropylene glycol (degree of polymerization = 2~10) phenyl ether (meth)acrylate (Meth)acrylate with polypropylene glycol structural units.

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

Examples of the lactone-modified (meth)acrylate having a hydroxyl group include adding a lactone to the (meth)acrylate having a hydroxyl group, and preferably adding caprolactone. The addition amount of caprolactone is preferably 1 mol~10 mol, more preferably 1 mol~5 mol. The aforementioned lactone-modified (meth)acrylate having a hydroxyl group is preferably a 1 mol adduct of caprolactone of 2-hydroxyethyl (meth)acrylate, or a caprolactone of 2-hydroxyethyl (meth)acrylate. 2 mol adduct, 3 mol adduct of caprolactone of 2-hydroxyethyl (meth)acrylate, 4 mol adduct of caprolactone of 2-hydroxyethyl (meth)acrylate, 2-(meth)acrylic acid 5 mol caprolactone adduct of hydroxyethyl ester, 10 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, etc.

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

The aforementioned (meth)acrylate having an oxygen-containing heterocyclic group is preferably a (meth)acrylate having an oxygen-containing heterocyclic group with a 4- to 6-membered ring. Specific examples of the (meth)acrylate having an oxygen-containing heterocyclic group include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acrylic acid (3-ethyloxy) Heterocyclobutan-3-yl)methyl ester, (meth)acrylic acid (2-methyl-2-ethyl-1,3-dioxocyclopentan-4-yl)methyl ester, cyclic trihydroxymethyl Propane formal (meth)acrylate, 2-[(2-tetrahydropyranyl)oxy]ethyl (meth)acrylate, 1,3-dioxane-(meth)acrylate, etc.

Examples of the acidic group include carboxyl group (-COOH), sulfonic acid group (-SO ₃ H), phosphate group (-OPO ₃ H ₂ ), phosphonic acid group (-PO ₃ H ₂ ), and phosphonite group (-PO ₂ H ₂ ). Examples of the (meth)acrylate having an acidic group include (meth)acrylate having a carboxyl group, (meth)acrylate having a phosphate group, and (meth)acrylate having a sulfonic acid group.

Examples of the (meth)acrylate having a carboxyl group include carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, and 2-maleic acid. -(Meth)acryloyloxyethyl ester, 2-(meth)acryloyloxyethyl phthalate is equal to (meth)acrylate with hydroxyl group, maleic anhydride, succinic anhydride, phthalate Acid anhydride and other acid anhydride reaction monomers, etc. Examples of the (meth)acrylate having a sulfonic acid group include ethyl (meth)acrylate sulfonate. Examples of the (meth)acrylate having a phosphate group include 2-(phosphonyloxy)ethyl (meth)acrylate.

The A block may have structural units other than the structural unit derived from a (meth)acrylic acid-based monomer. Other structural units that the A block may contain are not particularly limited as long as they are formed from a vinyl monomer copolymerizable with both a (meth)acrylic acid group monomer and a vinyl monomer that forms the B block described below. . The vinyl monomers that can form other structural units of the A block may be used alone or two or more types may be used in combination.

Specific examples of vinyl monomers that can form other structural units of the A block include α-olefins, aromatic vinyl monomers, heterocyclic-containing vinyl monomers, vinylamides, and vinyl carboxylates. Dienes, etc. These vinyl monomers may have hydroxyl groups or epoxy groups.

Examples of α-olefins include 1-hexene, 1-octene, 1-decene, and the like. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, and 2-methylstyrene. Hydroxymethylstyrene, 1-vinylnaphthalene, etc. Examples of the heterocyclic-containing vinyl monomer include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidinone, 2-vinylpyridine, and 4-vinylpyridine , N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, etc. Examples of vinylamides include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-caprolactamide, and the like. Examples of vinyl carboxylate include vinyl acetate, trimethylvinyl acetate, vinyl benzoate, and the like. Examples of dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, and the like.

The A block preferably contains a structural unit represented by the general formula (10), that is, it preferably contains a structural unit derived from the aforementioned lactone-modified (meth)acrylate having a hydroxyl group. The structural unit represented by general formula (10) has an ester bond part in the side chain and a terminal hydroxyl group, so it has high affinity with the dispersion medium and binder resin, and can improve the alkaline developability of the block copolymer.

[Chemical formula 2] [In general formula (10), n1 represents an integer from 1 to 10. R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 1 to 10 carbon atoms. R ³ represents an alkylene group having 1 to 10 carbon atoms. ]

n1 in the aforementioned formula (10) is preferably an integer from 1 to 7, more preferably an integer from 1 to 5.

The alkylene group having 1 to 10 carbon atoms represented by R ² may be either linear or branched, and is preferably linear. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ² include methylene, ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and heptamethylene. Methyl, octamethylene, nonamethylene, decamethylene, 1-methylethylidene, etc. R ² is preferably an alkylene group having 1 to 5 carbon atoms.

The alkylene group having 1 to 10 carbon atoms represented by R ³ may be either linear or branched, and is preferably linear. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ³ include methylene, ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and heptamethylene. Methyl, eight methylene, nine methylene, ten methylene, etc. R ³ is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 3 to 8 carbon atoms.

When the aforementioned A block contains the structural unit represented by the general formula (10), the content rate is preferably 10 mass% or more, more preferably 20 mass% or more, and still more preferably 30 mass% in 100 mass% of the A block. Above, it is particularly preferably 60 mass% or more, more preferably 95 mass% or less, more preferably 90 mass% or less, and still more preferably 85 mass% or less. By setting the content rate of the structural unit derived from the lactone-modified (meth)acrylate having a hydroxyl group within the above range, the alkaline developability of the block copolymer can be improved.

The A block preferably has a structural unit derived from a vinyl monomer having an acidic group (preferably (meth)acrylate or (meth)acrylic acid having an acidic group). Having a structural unit derived from a vinyl monomer with an acidic group can increase the solubility to alkaline developing solution and improve alkaline developability. However, if the ratio increases, the affinity with solvents and alkali-soluble resins may decrease. Therefore, the ratio of the structural units derived from the vinyl monomer having an acidic group is preferably such that the acid value of the entire block copolymer is lower than the amine value.

When a structural unit derived from a vinyl monomer having an acidic group is contained, the content rate is preferably 2 mass % or more, and more preferably 20 mass % or less in 100 mass % of the A block. If the content rate of the structural unit derived from the vinyl monomer having an acidic group is 2 mass % or more, the dissolution speed when neutralized with alkali in alkaline development is fast, and if it is 20 mass % or less, the hydrophilicity will not be If it is too high, the resulting pixel clutter can be suppressed.

In the aforementioned A block, the content rate of the structural unit represented by the general formula (1) described below is less than 10% by mass, preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.1% by mass or less. , the best one does not contain the structural unit shown in general formula (1). In the A block, the lower the content rate of the structural unit represented by the general formula (1), the better the dispersion performance of the coloring material can be improved.

The A block preferably does not have an amine group. That is, it is preferable that the vinyl monomer constituting the A block does not contain an amino group-containing vinyl monomer. If there are a large number of amine groups in the A block, when used as a dispersant, the coloring material will be adsorbed on both the A block and the B block, which will reduce the dispersion performance of the coloring material. In block A, the content rate of structural units derived from vinyl monomers having amine groups (including quaternized amine groups) is preferably 3% by mass or less, more preferably 1% by mass or less, and more preferably Preferably, it is 0.1 mass % or less, and the most optimum is 0 mass %.

When the A block contains two or more structural units, the various structural units contained in the A block may be contained in the A block in any form such as random copolymerization or block copolymerization. From the perspective of uniformity, it is preferable to Contains in random copolymer form. For example, the A block can be formed by a copolymer of a structural unit composed of an a1 block and a structural unit composed of an a2 block.

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

(Structural unit represented by general formula (1)) There may be only one type of structural unit represented by general formula (1), or two or more types may be present. Having a structural unit represented by the general formula (1) can improve adsorption with coloring materials and inhibit the generation of formaldehyde over time. In addition, among the structural units represented by the general formula (1), -Y ¹ -NR ¹¹ R ¹² bonded to X ¹ has a structure represented by the general formula (5).

[Chemical formula 3] [In the general formula (1), R ¹¹ represents a hydrogen atom and a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure. R ¹³ represents a hydrogen atom or a methyl group. X ¹ represents a amide group, an ester group, or a single bond. Y ¹ represents a divalent hydrocarbon group. ]

In the formula (1), R ¹¹ and R ¹² are synonymous with R ¹¹ and R ¹² in the aforementioned general formula (5). In the general formula (1), examples of the chain hydrocarbon group and the cyclic hydrocarbon group represented by R ¹¹ and R ¹² include those exemplified by R ¹¹ and R ¹² of the general formula (5). In the general formula (1), the linear alkyl group represented by R ¹¹ and R ¹² preferably has a carbon number of 2 to 20, more preferably a carbon number of 2 to 10, and more preferably a carbon number of 2 to 5. The chain alkyl group preferably has a carbon number of 3 to 20 carbon atoms, more preferably a carbon number of 3 to 10 carbon atoms, and still more preferably a carbon number of 3 to 5 carbon atoms.

The cyclic structure formed by the mutual bonding of R ¹¹ and R ¹² can be, for example, a nitrogen-containing heterocyclic ring with 5 to 7 members or a condensed ring formed by the condensation of two of these rings. The nitrogen-containing heterocyclic ring is preferably not aromatic, and more preferably is a saturated ring. Specific examples include structures represented by the following formulas (1-1), (1-2), and (1-3).

[Chemical formula 4] [In general formulas (1-1), (1-2), and (1-3), R14 represents an alkyl group having 1 to 6 carbon atoms. l represents an integer from 0 to 5. m represents an integer from 0 to 4. n represents an integer from 0 to 4. *Indicates bonding. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, the plural R14s may be the same or different. ]

The aforementioned X1 represents a amide group (-CO-NH-), an ester group (-CO-O-), or a single bond. In addition, the bonding direction of the amide group and the ester group is not particularly limited. Examples of the bonding form of the amide group include C-CO-NH-Y1 or C-NH-CO-Y1, and C-CO-NH-Y1 is preferred. Examples of the bonding state of the ester group include C-CO-O-Y1 or C-O-CO-Y1, and C-CO-O-Y1 is preferred.

In the general formula (1), Y ¹ is synonymous with Y ¹ in the aforementioned general formula (5). The aforementioned Y ¹ is preferably an alkylene group having 1 to 10 carbon atoms. The aforementioned alkylene group may be either linear or branched, and is preferably linear. Y ¹ is preferably an alkylene group having 1 to 5 carbon atoms.

Specific examples of the vinyl monomer forming the structural unit represented by the general formula (1) include ethylaminoethyl (meth)acrylate, ethylaminopropyl (meth)acrylate, and ethylamine (meth)acrylate. Butyl ester, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, propylaminoethyl (meth)acrylate, Allylaminopropyl (meth)acrylate, Allylaminobutyl (meth)acrylate, Dipropylaminoethyl (meth)acrylate, Dipropylaminopropyl (meth)acrylate, Dipropylaminopropyl (meth)acrylate Butyl ester, tert-butylaminoethyl (meth)acrylate, etc.

The content rate of the structural unit represented by the general formula (1) is preferably 10 mass% or more, more preferably 30 mass% or more, more preferably 50 mass% or more, and more preferably 98 mass% in 100 mass% of the B block % or less, more preferably 80 mass% or less, further preferably 70 mass% or less. By setting the content rate of the structural unit represented by the general formula (1) within this range, high affinity with the coloring material can be achieved.

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

[Chemical formula 5] [In the general formula (2), R21 represents a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent. R22 and R23 each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R22 and R23 can bond with each other to form a cyclic structure. R24 represents a hydrogen atom or a methyl group. X2 represents a amide group, an ester group, or a single bond. Y2 represents a divalent hydrocarbon group. ]

Examples of the chain hydrocarbon group represented by R ²¹ to R ²³ include linear alkyl groups, branched chain alkyl groups, and the like. The linear alkyl group preferably has a carbon number of 1 to 20, more preferably a carbon number of 2 to 20, still more preferably a carbon number of 2 to 10, and particularly preferably a carbon number of 2 to 5. Examples of the linear alkyl group include ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-lauryl, and the like. The branched alkyl group preferably has a carbon number of 3 to 20 carbon atoms, more preferably a carbon number of 3 to 10 carbon atoms, and still more preferably a carbon number of 3 to 5 carbon atoms. Examples of the branched alkyl group include isopropyl, isobutyl, second butyl, third butyl, 2-ethylhexyl, neopentyl, isooctyl, and the like.

Examples of the substituents of the chain hydrocarbon group represented by R ²¹ to R ²³ include a halo group, an alkoxy group, a benzyl group (-COC ₆ H ₅ ), a hydroxyl group, and the like.

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

Examples of the substituents of the cyclic hydrocarbon group represented by R ²¹ to R ²³ include a halo group, an alkoxy group, a chain alkyl group, a hydroxyl group, and the like.

The cyclic structure formed by the mutual bonding of R ²² and R ²³ can be, for example, a nitrogen-containing heterocyclic ring with 5 to 7 members or a condensed ring formed by the condensation of two of these rings. The nitrogen-containing heterocyclic ring is preferably not aromatic, and more preferably is a saturated ring. Specific examples include structures represented by the following formulas (2-1), (2-2), and (2-3).

[Chemical formula 6] [In general formulas (2-1), (2-2), and (2-3), R25 is R21. R26 represents an alkyl group having 1 to 6 carbon atoms. l represents an integer from 0 to 5. m represents an integer from 0 to 4. n represents an integer from 0 to 4. *Indicates bonding. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, the plural R26s may be the same or different. ]

The aforementioned X ² represents a amide group (-CO-NH-), an ester group (-CO-O-), or a single bond. In addition, the bonding direction of the amide group and the ester group is not particularly limited. Examples of the bonding state of the amide group include C-CO-NH-Y ² or C-NH-CO-Y ² , with C-CO-NH-Y ² being preferred. Examples of the bonding form of the ester group include C-CO-OY ² or CO-CO-Y ² , with C-CO-OY ² being preferred.

Examples of the divalent hydrocarbon group represented by Y ² include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, and an aromatic hydrocarbon diyl group having 6 to 10 carbon atoms. Among these, an alkylene group having 1 to 10 carbon atoms is preferred. The aforementioned alkylene group may be either linear or branched, and is preferably linear. Y ² is preferably an alkylene group having 1 to 5 carbon atoms.

Examples of Z ^- include halogen anions, carboxylate anions, sulfate anions, sulfonate anions, phosphate anions, and nitroxide radical anions. Examples of the halogen anion include fluoride anion, chlorine anion, bromine anion and iodine anion. Examples of the carboxylate anions include alkyl carboxylate anions such as acetate anions and propionate anions; and aromatic carboxylate anions such as benzoic acid anions. Examples of the sulfate anion include alkyl sulfate anions such as methyl sulfate anion and ethyl sulfate anion; and aromatic sulfate anions such as phenyl sulfate anion and benzyl sulfate anion. Examples of the sulfonate anion include alkylsulfonate anions such as methanesulfonate anion and ethanesulfonate anion; aromatic sulfonate anions such as benzene sulfonate anion and toluenesulfonate anion; and the like. Examples of the phosphate anion include alkyl phosphate anions such as methylphosphonic acid anion and ethylphosphonic acid anion; and aromatic phosphate anions such as phenylphosphonic acid anion and benzylphosphonic acid anion.

Specific examples of the vinyl monomer forming the structural unit represented by the aforementioned formula (2) include (meth)acryloxyethylbenzyldiethyl ammonium chloride and (meth)acryloxypropyl Benzyldiethyl ammonium chloride, (meth)acryloxybutylbenzyldiethyl ammonium chloride, (meth)acryloxyethylbenzyldiethylammonium bromide, (meth)acryloxyethylbenzyldiethylammonium bromide )Acryloxypropylbenzyldiethyl ammonium bromide, (meth)acryloxybutylbenzyldiethyl ammonium bromide, (meth)acryloxyethylbenzyldiethyl ammonium bromide Ammonium iodide, (meth)acryloxypropylbenzyldiethyl ammonium iodide, (meth)acryloxybutylbenzyldiethylammonium iodide, (meth)acryloxy Ethyl benzyl diethyl ammonium fluoride, (meth)acryloxypropyl benzyl diethyl ammonium fluoride, (meth)acryloxy butyl benzyl diethyl ammonium fluoride, etc.

When the structural unit represented by the general formula (2) is contained, the content rate in 100 mass% of the B block is preferably 2 mass% or more, more preferably 20 mass% or more, preferably 90 mass% or less, and more preferably 70% by mass or less. By setting the content of the structural unit represented by the general formula (2) within this range, high affinity with the coloring material can be achieved.

The B block may contain only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may contain other structural units. From the viewpoint of maintaining affinity with the colored material, the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the B block is relatively high in 100 mass % of the B block. Preferably, it is 80 mass % or more, More preferably, it is 90 mass % or more, Still more preferably, it is 95 mass % or more. Moreover, it is preferable that the B block does not substantially contain a structural unit derived from a vinyl monomer having an acidic group. That is, the content rate of the structural unit derived from the vinyl monomer having an acidic group is preferably 5 mass% or less, more preferably 2 mass% or less in 100 mass% of the B block.

Specific examples of vinyl monomers that can form other structural units of the B block are the same as those described for specific examples of vinyl monomers that can form other structural units of the A block.

When the B block contains two or more structural units, the various structural units contained in the B block can be contained in the B block in any form such as random copolymerization or block copolymerization. From the perspective of uniformity, it is preferable to Contains in random copolymer form. For example, the B block can be formed by a copolymer of a structural unit composed of a b1 block and a structural unit composed of a b2 block.

(block copolymer) The structure of the aforementioned block copolymer is preferably a linear block copolymer. In addition, the linear block copolymer may have any structure (arrangement). However, from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the A block is represented by A and the B block is represented by B. When, it is preferable to have at least one structure selected from the group consisting of (A-B)m type, (A-B)m-A type, and (B-A)m-B type (m is an integer of 1 or more, for example, 1 to 3). things. From the viewpoint of workability during processing and physical properties of the composition, the A-B type diblock copolymer is preferred among these. By constituting the A-B type diblock copolymer, it is possible to have both the structural unit derived from the (meth)acrylic monomer in the A block and the structural unit represented by the general formula (1) in the B block. It is localized and can effectively act on coloring materials, dispersion media (solvents), and binder resins (alkali-soluble resins). The block copolymer may have blocks other than the A block and the B block.

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

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

When the block copolymer contains a structural unit having an acidic group, the content rate of the structural unit derived from the vinyl monomer having an acidic group in the block copolymer is preferably 1 mass % or more, preferably 10 mass% or less.

In the aforementioned block copolymer, the total content rate of the structural unit represented by the aforementioned general formula (1) and the aforementioned structural unit represented by the aforementioned general formula (2) is preferably 5 mass % or more, more preferably 10 mass % or more, and more preferably Preferably, it is 20 mass % or more, More preferably, it is 50 mass % or less, More preferably, it is 45 mass % or less, Still more preferably, it is 40 mass % or less.

The molecular weight of the aforementioned block copolymer was measured by gel permeation chromatography (hereinafter referred to as "GPC"). The weight average molecular weight (Mw) of the aforementioned block copolymer is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, particularly preferably 6,000 or more, preferably 40,000 or less, more preferably 30,000 or less, and still more preferably The best price is less than 25,000, and the best price is less than 20,000. If the weight average molecular weight is within the above range, the dispersion performance when used as a dispersant will be better.

The molecular weight distribution (PDI) of the block copolymer is preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.6 or less. Furthermore, in the present invention, the molecular weight distribution (PDI) is determined by (weight average molecular weight (Mw) of the block copolymer)/(number average molecular weight (Mn) of the block copolymer). The smaller the PDI, the narrower the molecular weight distribution width. It is a copolymer with concentrated molecular weight. When its value is 1.0, the molecular weight distribution width is the narrowest. That is, the lower limit of PDI is 1.0. If the molecular weight distribution (PDI) of the block copolymer exceeds 2.5, it includes those with small molecular weights and those with large molecular weights.

From the viewpoint of adsorption of coloring materials and dispersion of coloring materials, the amine value of the block copolymer is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, and still more preferably 80 mgKOH/g or more. It is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, still more preferably 120 mgKOH/g or less.

When the block copolymer contains a structural unit having an acidic group, the acid value of the block copolymer is preferably 5 mgKOH/g or more, and preferably 50 mgKOH/g or less. By setting the acid value within this range, it is possible to appropriately interact with the binder resin (alkali-soluble resin) without impairing the affinity between the block copolymer and the coloring material.

(Production method of block copolymer) Methods for producing the aforementioned block copolymers include: first producing the A block through polymerization of vinyl monomers, and then polymerizing the monomers of the B block in the A block; first producing the B block, and then polymerizing the B block in the A block. The method of polymerizing the monomer of the A block in the B block; the method of coupling the A block and the B block after separately manufacturing the A block and the B block, etc.

The polymerization method is not particularly limited, but living radical polymerization is preferred. That is, the block copolymer is preferably polymerized by living radical polymerization. In the conventional free radical polymerization method, not only the initial reaction and growth reaction will cause the deactivation of the growth terminal, but also the stop reaction and chain transfer reaction will cause the deactivation of the growth terminal. It is easy to form a mixture of polymers with various molecular weights and heterogeneous compositions. tendency. In this regard, the living radical polymerization method not only maintains the simplicity and versatility of previous radical polymerization methods, but also does not easily cause stop reactions or chain transfer. It can grow without deactivation at the growth end, so it is easy to manufacture polymers with precise molecular weight distribution control and composition. A homogeneous polymer is preferred in this regard.

Among the living radical polymerization methods, there are different methods of stabilizing the long end of the polymerization, including the method of using a transition metal catalyst (ATRP method); the method of using a sulfur-based reversible chain transfer agent (RAFT method); and the use of an organic tellurium compound. method (TERP method) and other methods. The ATRP method uses an amine complex, so sometimes it cannot be used without protecting the acidic group of the vinyl monomer with the acidic group. The RAFT method is difficult to form a low molecular weight distribution when using multiple monomers, and has problems such as sulfur odor or coloration. Among these methods, the TERP method is preferably used from the viewpoint of using monomer diversity, molecular weight control in the polymer field, uniform composition, or coloring.

The TERP method refers to a method that uses an organic tellurium compound as a chain transfer agent to polymerize a radically polymerizable compound (vinyl monomer), for example, International Publication No. 2004/14848, International Publication No. 2004/14962, and International Publication No. 2004/ 072126, and the method described in International Publication No. 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d). (a) Polymerize a vinyl monomer using an organic tellurium compound represented by the general formula (3). (b) Polymerize a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator. (c) Polymerizing a vinyl monomer using a mixture of an organic telluride compound represented by the general formula (3) and an organic ditelluride compound represented by the general formula (4). (d) Polymerize a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (3), an azo polymerization initiator, and an organic ditelluride compound represented by the general formula (4).

[Chemical Formula 7] [In the general formula (3), R ³¹ represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms. R ³² and R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ³⁴ represents an alkyl group, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, acyl group, amide group, oxycarbonyl group, cyano group, allyl group or propargyl group having 1 to 8 carbon atoms. In the general formula (4), R ³¹ represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms. ]

The group represented by R ³¹ is an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms, and is specifically as follows. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, pentyl, hexyl, and heptyl , linear or branched chain alkyl groups such as octyl, or cyclic alkyl groups such as cyclohexyl, etc. Preferably it is a linear or branched chain alkyl group having 1 to 4 carbon atoms, and more preferably it is a methyl or ethyl group. Examples of the aryl group include phenyl group, naphthyl group, and the like. Examples of the aromatic heterocyclic group include pyridyl, furyl, thienyl, and the like.

The groups represented by R ³² and R ³³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The specific details of each group are as follows. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, pentyl, hexyl, and heptyl , linear or branched chain alkyl groups such as octyl, or cyclic alkyl groups such as cyclohexyl, etc. Preferably it is a linear or branched chain alkyl group having 1 to 4 carbon atoms, and more preferably it is a methyl or ethyl group.

The group represented by R ³⁴ is an alkyl group, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, amide group, amide group, oxycarbonyl group, cyano group, allyl group or alkyne with 1 to 8 carbon atoms. Propyl group is specifically as follows. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, pentyl, hexyl, and heptyl , octyl and other linear or branched chain alkyl groups, cyclohexyl and other cyclic alkyl groups, etc. Preferably it is a linear or branched chain alkyl group having 1 to 4 carbon atoms, more preferably a methyl or ethyl group. Examples of the aryl group include phenyl group, naphthyl group, and the like. Preferred is phenyl. Examples of the substituted aryl group include a phenyl group having a substituent, a naphthyl group having a substituent, and the like. Examples of the substituent of the aryl group having a substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl group-containing group represented by -COR ³⁴¹ (R ³⁴¹ is a group having 1 to 8 carbon atoms). Alkyl group, aryl group, alkoxy group or aryloxy group with 1 to 8 carbon atoms), sulfonyl group, trifluoromethyl group, etc. In addition, one or two of these substituents may be substituted. Examples of the aromatic heterocyclic group include pyridyl, furyl, thienyl, and the like. The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, butyl Oxygen, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, etc. Examples of the acyl group include an acetyl group, a propyl group, a benzyl group, and the like. Examples of the amide group include -CONR ³⁴²¹ R ³⁴²² (R ³⁴²¹ and R ³⁴²² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group). The oxycarbonyl group is preferably a group represented by -COOR ³⁴³¹ (R ³⁴³¹ is a hydrogen atom, an alkyl group with 1 to 8 carbon atoms, or an aryl group), and examples thereof include carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, and propoxycarbonyl group. , n-butoxycarbonyl, second butoxycarbonyl, third butoxycarbonyl, n-pentyloxycarbonyl, phenoxycarbonyl, etc. Preferred oxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl. Examples of allyl groups include -CR ³⁴⁴¹ R ³⁴⁴² -CR ³⁴⁴³ =CR ³⁴⁴⁴ R ³⁴⁴⁵ (R ³⁴⁴¹ and R ³⁴⁴² are each independently a hydrogen atom or an alkyl group with 1 to 8 carbon atoms, and R ³⁴⁴³ , R ³⁴⁴⁴ and R ³⁴⁴⁵ are each independently It is a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and each substituent can be connected in a ring structure), etc. Examples of the propargyl group include -CR ³⁴⁵¹ R ³⁴⁵² -C≡CR ³⁴⁵³ (R ³⁴⁵¹ and R ³⁴⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ³⁴⁵³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, Aryl or silicone), etc.

Specific examples of the organic tellurium compound represented by the general formula (3) include (methyltellurylmethyl)benzene, (methyltellurylmethyl)naphthalene, and ethyl-2-methyl-2-methyltellurium -Propionate, ethyl-2-methyl-2-n-butyltelluryl-propionate, (2-trimethylsiloxyethyl)-2-methyl-2-methyltelluryl- Propionate, (2-hydroxyethyl)-2-methyl-2-methyltelluryl-propionate, or (3-trimethylsilylpropargyl)-2-methyl-2-methyl All organic tellurium compounds described in International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and International Publication No. 2004/096870, etc.

Specific examples of the organic ditelluride compound represented by the general formula (4) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, and bicyclic ditelluride. Propyl ditelluride, di-n-butyl ditelluride, di-second butyl ditelluride, di-tert-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis-( p-methoxyphenyl)ditelluride, bis-(p-aminophenyl)ditelluride, bis-(p-nitrophenyl)ditelluride, bis-(p-cyanophenyl)ditelluride, Bis-(p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride or dipyridyl ditelluride, etc.

As the azo polymerization initiator, any azo polymerization initiator commonly used in radical polymerization can be used without particular limitation. Examples include 2,2'-azobis(isobutyronitrile)(AIBN), 2,2'-azobis(2-methylbutyronitrile)(AMBN), 2,2'-azobis(2 ,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis(1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2'-azobisisobutyrate (MAIB), 4,4'-azobis(4-cyanovaleric acid) (ACVA), 1,1'-azobis(1-acetyloxy-1-phenylethane), 2, 2'-Azobis(2-methylbutylamide), 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70), 2, 2'-Azobis(2-methylformamidinopropane) dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'- Azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2,4,4-trimethylpentane), 2-cyano- 2-propyl azoformamide, 2,2'-azobis(N-butyl-2-methylpropanamide), or 2,2'-azobis(N-cyclohexyl-2- Methylpropamide), etc.

The polymerization step is to mix the vinyl monomer and the organic tellurium compound of the general formula (3) in a container replaced by an inert gas, and further mix azo based on the type of the vinyl monomer for the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution, etc. It is a polymerization initiator and/or an organic ditelluride compound of general formula (4). At this time, examples of the inert gas include nitrogen, argon, helium, and the like. Preferred are argon and nitrogen.

In the above (a), (b), (c) and (d), the amount of vinyl monomer used may be appropriately adjusted according to the physical properties of the target copolymer. Preferably, the vinyl monomer is 5 mol to 10000 mol based on 1 mol of the organic tellurium compound of general formula (3).

When the organic tellurium compound of the general formula (3) and an azo polymerization initiator are used together in the above (b), the azo polymerization initiator is preferably 0.01 mol relative to 1 mol of the organic tellurium compound of the general formula (3). ~10mol.

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

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

The polymerization reaction can be carried out even without a solvent, and the aforementioned mixture can be stirred using an aprotic solvent or a protic solvent generally used in radical polymerization to carry out the polymerization reaction. Examples of aprotic solvents that can be used include anisole, benzene, toluene, N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), acetone, and 2-butanone (methyl Ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, or trifluoromethylbenzene, etc. Examples of protic solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosole, butyl cellosole, 1-methoxy-2-propanol, hexafluoroisopropanol, or Diacetone alcohol, etc.

The amount of solvent used can be adjusted appropriately. For example, based on 1 g of vinyl monomer, it is preferably 0.01 ml or more, more preferably 0.05 ml or more, more preferably 0.1 ml or more, preferably 50 ml or less, and more preferably 10 ml or less. , and preferably less than 1ml.

The reaction temperature and reaction time can be appropriately adjusted according to the molecular weight or molecular weight distribution of the obtained copolymer, usually stirring at 0°C to 150°C for 1 minute to 100 hours. The TERP method can obtain high yields and precise molecular weight distribution even at low polymerization temperatures and short polymerization times. At this time, the pressure is usually normal pressure, but it may be pressurized or reduced.

After the polymerization reaction is completed, the solvent used, residual vinyl monomer, etc. are removed from the obtained reaction mixture by general separation and purification means, and the target copolymer can be separated.

The growing end of the copolymer obtained by the polymerization reaction is in the form of -TeR ³¹ (in the formula, R ³¹ is the same as above) derived from the tellurium compound. After the polymerization reaction is completed, it will be deactivated when operated in the air, but tellurium atoms will remain. . Copolymers with tellurium atoms remaining at the terminals will be colored or have poor thermal stability, so it is better to remove the tellurium atoms.

Methods for removing tellurium atoms can be used: Free radical reduction method using tributylstannane or thiol compounds; Adsorption methods using activated carbon, silica gel, activated alumina, activated clay, molecular sieves and polymer adsorbents; Methods of adsorbing metals using ion exchange resin, etc.; Add peroxides such as hydrogen peroxide or benzyl peroxide, or blow air or oxygen into the system to oxidize and decompose the tellurium atoms at the end of the copolymer. Combine with water washing or appropriate solvents to remove residual tellurium compounds. Liquid-liquid extraction method or solid-liquid extraction method; Purification methods in a solution state such as ultrafiltration to remove only those with a specific molecular weight; In addition, these methods can be used in combination.

Moreover, the other end (the end opposite to the growth end) of the copolymer obtained by the polymerization reaction is -CR ³² R ³³ R ³⁴ derived from the tellurium compound (wherein R ³² , R ³³ and R ³⁴ are the same as the formula) R ³² , R ³³ and R ³⁴ in (3) are the same) form.

When the tertiary amino group of the structural unit represented by the formula (1) is quaternized, examples of the quaternization agent include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, and methyl iodide; benzyl chloride, benzyl bromide, benzyl Aralkyl halides such as base iodide; dimethyl sulfate; diethyl sulfate, di-n-propyl sulfate and other dialkyl sulfates, etc. Among these, aralkyl halides such as benzyl chloride, benzyl bromide and benzyl iodide are preferred, and benzyl chloride is more preferred. The structure after quaternization introduces alkyl and aralkyl groups derived from the quaternization agent. Therefore, the amount of the structural unit represented by the formula (2) can be estimated by measuring the amount of the alkyl group and aralkyl group introduced by the quaternary transformation.

A method of quaternizing the tertiary amine structure that is part of the structural unit represented by formula (1) in the polymer includes 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 represented by formula (1), and then adding a quaternizing agent to the reaction solution and stirring. The preferred reaction solution temperature for adding the quaternary agent is 55°C to 65°C, and the preferred stirring time is 5 to 20 hours. When adding a quaternary agent, it is preferred to dilute the reaction solution after polymerization. Examples of the solvent added for dilution include solvents that can be used in polymerization reactions. Preferably, they are protic solvents, and more preferably, methanol is used.

(polymer product) In the aforementioned dispersant composition, a polymerization product containing the aforementioned block copolymer can be used as the dispersant component. The polymerization product refers to a product obtained by performing a polymerization operation (quaternary treatment if necessary) in order to obtain the block copolymer. The polymerization product contains the desired block copolymer and polymer impurities that are by-products when synthesizing the block copolymer.

The aforementioned polymer impurities refer to other polymers that are inevitable by-products during the synthesis of the desired block copolymer. For example, when synthesizing an A-B diblock copolymer, by-product polymer impurities include random polymers with the same composition as the A block and random polymers with the same composition as the B block. In addition, polymer impurities are polymers that are by-products during the synthesis of the desired block copolymer, excluding additionally added polymers.

In the polymerization product, the content of the block copolymer is preferably 50 mass% or more based on 100 mass% of the polymerization product. If the content of the block copolymer in the polymerization product is 50% by mass or more, the dispersion performance can be improved when the polymerization product is used as a dispersant.

(dispersed media) The aforementioned dispersant composition may contain a dispersion medium. The aforementioned dispersion medium can be appropriately selected and used as long as it can disperse or dissolve the block copolymer, does not react with these components, and has moderate volatility. For example, conventionally known organic solvents can be used, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxy Methylpentanol, methoxypropanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether Glycol monoalkyl ethers such as 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, diethyl acetate Glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol mono Ethyl ether acetate, 3-methyl-3-methoxybutyl acetate and other glycol alkyl ether acetates; ethylene glycol diacetate, 1,3-butanediol diacetate, Diol diacetates such as 1,6-hexanediol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, propyl ether, diethyl ether, dipropyl ether, Diisopropyl ether, butyl ether, dipyl ether, ethyl isobutyl ether, dihexyl ether and other ethers; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isopentyl ether Ketones, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentanone, methyl butanone, methyl hexanone, methyl nonanone, methoxymethyl pentanone and other ketones Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerol, benzyl alcohol, etc. ; Aliphatic hydrocarbons such as n-pentane, n-octane, isobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; cyclohexane, methylcyclohexane, methylcyclohexane Alicyclic hydrocarbons such as alkenes and dicyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, and amyl acetate. Ester, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate Ester, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methyl Chain or cyclic esters such as propyloxypropionate, 3-methoxybutylpropionate, and γ-butyrolactone; alkoxy groups such as 3-methoxypropionic acid and 3-ethoxypropionic acid Carboxylic acids; halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile.

The content of the dispersion medium in the aforementioned dispersant composition can be adjusted appropriately and is not particularly limited. In the dispersant composition, the upper limit of the dispersion medium content is usually 99% by mass. In addition, considering the viscosity suitable for producing the coloring composition described below, the lower limit of the dispersion medium content in the dispersant composition is usually 10% by mass, and preferably 30% by mass.

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

(coloring materials) The type of the coloring material can be appropriately selected according to its use, and examples thereof include pigments and dyes. From the viewpoint of light resistance and heat resistance, the coloring composition preferably contains a pigment as a coloring material. The pigment may be either an organic pigment or an inorganic pigment, but an organic pigment containing an organic compound as a main component is particularly preferred. Examples of the pigment include various pigments such as red pigments, yellow pigments, orange pigments, blue pigments, green pigments, and purple pigments. Examples of the pigment structure include azo pigments such as monoazo pigments, diazo pigments, and condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanin pigments, isoindolinone pigments, and isotopyrroline pigments. Polycyclic pigments such as indoline pigments, quinacridone pigments, indigo pigments, thioindigo pigments, quinoline yellow pigments, bisoxazine pigments, anthraquinone pigments, perylene pigments, and purple ring ketone pigments Department of pigments, etc. The coloring composition may contain only one type of pigment or a plurality of types.

Specific examples of the pigment include C.I. Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81:2, 81:3, 122, 123, 146, 149, 166, 168, 177, 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264, 269 and other red pigments; C.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, 150, 151, 154, 155, 166, 167, 168, 170, 180, 185, 188, 193, 194, 213 and other yellow pigments; C.I. Pigment Orange 36, 38, 43 and other orange pigments; C.I. Pigment Blue 15, 15:2, 15:3, 15:4, 15: 6, 16, 22, 60 and other blue pigments; C.I. Pigment Green 7, 36, 58, 59, 62, 63, aluminum phthalocyanin, polyhalogenated aluminum phthalocyanin, aluminum phthalocyanin hydroxide, Phenoxyphosphinoaluminum phthalocyanin, diphenylphosphinoaluminum phthalocyanin, polyhalogenated diphenoxyphosphinoaluminum phthalocyanin, polyhalogenated diphenylphosphinoaluminum phthalocyanin and other green Pigments; C.I. Pigment Violet 23, 32, 50 and other purple pigments, etc. Among these, preferred pigments are C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment Blue 15, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 16, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, etc.

When the colored composition of the present invention is used to form a light-shielding material such as a black matrix of a color filter, a black pigment can be used. The black pigment can be used alone, or the above-mentioned red pigment, the above-mentioned green pigment, the above-mentioned blue pigment, etc. can be mixed and used. Examples of the black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black, and the like. From the viewpoint of light shielding rate and image characteristics, carbon black and titanium black are preferred among these.

The average particle diameter of the aforementioned coloring material can be appropriately selected depending on its use and is not particularly limited. From the viewpoint of high transparency and high contrast, the coloring composition preferably contains a coloring material with an average particle diameter of 10 nm to 150 nm.

The coloring material may contain a pigment derivative as a dispersion aid. In order to be ion-bonded and adsorbed to the amine group in the polymer contained in the dispersant composition, the aforementioned pigment derivative is preferably an acidic pigment derivative containing an acidic group. The pigment derivative is one in which an acidic functional group is introduced into the pigment skeleton. The pigment skeleton is preferably the same as or similar to the coloring material constituting the coloring composition, or the same or similar skeleton to the compound of the pigment raw material. Specific examples of the pigment skeleton include an azo pigment skeleton, a phthalocyanin pigment skeleton, an anthraquinone pigment skeleton, a triazine pigment skeleton, an acridine pigment skeleton, and a perylene pigment skeleton. The acidic group introduced into the pigment skeleton is preferably a carboxyl group, a phosphate group, or a sulfonic acid group. In addition, from the viewpoint of synthesis convenience and acidity strength, a sulfonic acid group is preferred. In addition, the acidic group can be directly bonded to the pigment skeleton, or can be bonded to the pigment skeleton through hydrocarbon groups such as alkyl or aryl groups; ester, ether, sulfonamide, or urethane bonds. The usage amount of the pigment derivative is not particularly limited, but for example, it is preferably 4 to 17 parts by mass relative to 100 parts by mass of the coloring material.

From the viewpoint of brightness, the upper limit of the coloring material content in the coloring composition is usually 80 mass%, preferably 70 mass%, and more preferably 60 mass% in the total solid content of the coloring composition. In addition, the lower limit of the coloring material content in the coloring composition is usually 10% by mass, preferably 20% by mass, and more preferably 30% by mass based on the total solid content of the coloring composition. The solid content here refers to components other than the dispersion medium described below.

The content of the dispersant component (block copolymer and polymerization product) relative to the coloring material in the coloring composition is preferably 5 to 200 parts by mass, more preferably 10 to 10 parts by mass based on 100 parts by mass of the coloring material. 100 parts by mass, and more preferably 10 parts by mass to 80 parts by mass.

(Binder resin) The aforementioned coloring composition contains a binder resin (except for the aforementioned polymer having a structure represented by the general formula (5) in the side chain). This can improve the alkaline developability of the colored composition or the adhesion to the substrate. The binder resin is not particularly limited, but is preferably a resin having an acidic group such as a carboxyl group or a phenolic hydroxyl group.

The binder resin is preferably a random copolymer containing a structural unit derived from a carboxyl group-containing vinyl monomer and a structural unit derived from (meth)acrylate. The aforementioned carboxyl group-containing vinyl monomer is preferably (meth)acrylic acid. Examples of the (meth)acrylate include methyl (meth)acrylate, butyl (meth)acrylate, and benzyl (meth)acrylate.

In the aforementioned binder resin, the total content rate of structural units derived from carboxyl group-containing vinyl monomers and structural units derived from (meth)acrylate is preferably 50 mass % or more, more preferably 60 mass % or above, and more preferably 70% by mass or more. Moreover, in the aforementioned binder resin, the content rate of the structure derived from the carboxyl 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 still more preferably It is 90 mass % or less, more preferably, it is 70 mass % or less.

Preferred among these is a random copolymer of a carboxyl group-containing vinyl monomer and (meth)acrylate. 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)acrylic acid Random copolymers with butyl (meth)acrylate and benzyl (meth)acrylate, etc. From the viewpoint of affinity between the binder resin and the colored material, a particularly preferred binder resin is a random copolymer of (meth)acrylic acid and benzyl (meth)acrylate.

In the copolymer of a carboxyl group-containing vinyl monomer and (meth)acrylate, the (meth)acrylic acid content in all monomer components is usually 5 mass% to 90 mass%, preferably 10 mass% to 70 mass% mass%, more preferably 20 mass% to 70 mass%.

The aforementioned binder resin may have a radical polymerizable carbon-carbon double bond in the side chain. By having a double bond in the side chain, the photocurability of the coloring composition of the present invention is improved, so the resolution and adhesion can be further improved. Methods for introducing radically polymerizable carbon-carbon double bonds into the side chain include, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, ortho (or m or (p) vinyl benzyl glycidyl ether and other compounds react with the acidic groups of the aforementioned binder resin.

The Mw of the binder resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 20,000. If the Mw of the binder resin is 3,000 or more, the colored layer formed by the colored composition will have good heat resistance, film strength, etc., and if the Mw is 100,000 or less, the alkaline developability of the coating film will be better.

The acid value of the binder resin is preferably 20mgKOH/g~170mgKOH/g, more preferably 50mgKOH/g~150mgKOH/g, and still more preferably 90mgKOH/g~150mgKOH/g. If the acid value of the binder resin is 20 mgKOH/g or more, the alkali developability of the colored composition to form a colored layer will be better, and if it is 170 mgKOH/g or less, the heat resistance will be good.

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

(cross-linking agent) The aforementioned coloring composition may contain a crosslinking agent if necessary. Cross-linking agents are compounds with two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxirane group, an oxetanyl group, an N-alkoxymethylamino group, and the like. The cross-linking agent is preferably a compound having two or more (meth)acrylyl groups, or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth)acrylyl groups include polyfunctional (meth)acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, and caprolactone-modified polyester. Functional (meth)acrylate, alkylene oxide modified multifunctional (meth)acrylate, multifunctional urethane (meth)acrylate obtained by reacting (meth)acrylate with hydroxyl group and multifunctional isocyanate Ester, polyfunctional (meth)acrylate with carboxyl group obtained by reacting (meth)acrylate with hydroxyl group and acid anhydride, etc.

Examples of the aforementioned aliphatic polyhydroxy compounds include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerin, trimethylolpropane, neopentylerythritol, dineopenterythritol, etc. Aliphatic polyhydroxy compounds with trivalent or higher valence. Examples of the aforementioned (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, neopenterythritol tri(meth)acrylate, and dimethacrylate. Neopenterythritol penta(meth)acrylate, dineopenterythritol hexa(meth)acrylate, glycerol di(meth)acrylate, etc. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. Examples of the aforementioned acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; Anhydride, diphenylketone tetracarboxylic dianhydride and other tetrabasic acid dianhydrides.

In the aforementioned coloring composition, the content of the cross-linking agent is preferably 10 to 1,000 parts by mass, and more preferably 20 to 500 parts by mass relative to 100 parts by mass of the coloring material. If the cross-linking agent content is too small, sufficient hardening properties may not be obtained. On the other hand, if the amount of cross-linking is too high, the alkali developability of the colored composition of the present invention will be reduced, and smearing, film residue, etc. will tend to occur on the unexposed substrate or the light-shielding layer.

(Photopolymerization initiator) The aforementioned coloring composition may contain a photopolymerization initiator if necessary. This can impart physical radiation properties to the colored composition. The aforementioned photopolymerization initiator is a compound that generates active species that can initiate polymerization of the cross-linking agent by being exposed to radiation such as visible rays, ultraviolet rays, far-infrared rays, electron rays, and X-rays.

Examples of the photopolymerization initiator include thioxanthone-based compounds, acetophenone-based compounds, diimidazole-based compounds, triazine-based compounds, O-acyl oxime-based compounds, onium salt-based compounds, benzoin-based compounds, and diphenyl. Ketone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, acyl imine sulfonate compounds, aminoketone compounds, etc. The photopolymerization initiator can be used alone or in mixture of two or more types.

In the colored composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, and more preferably 1 to 100 parts by mass relative to 100 parts by mass of the cross-linking agent. At this time, if the content of the photopolymerization initiator is too small, exposure curing may be insufficient. On the other hand, if it is too large, a colored layer may be formed that tends to peel off from the substrate during development.

(dispersed media) The aforementioned coloring composition may contain a dispersion medium. The aforementioned dispersion medium can be appropriately selected and used as long as it can disperse or dissolve other components constituting the coloring composition, does not react with these components, and has moderate volatility. For example, conventionally known organic solvents can be used, and examples thereof include organic solvents (dispersion media) that can be used for the aforementioned dispersant composition. From the viewpoints of dispersibility of pigments, dispersant solubility, and coatability of the pigment-dispersed composition, the organic solvent is preferably glycol alkyl ether acetate, monohydric or polyhydric alcohols. The solvent contained in the pigment dispersion composition may be only one type or a plurality of types.

When the pixels of the color filter are formed by photolithography, the boiling point of the aforementioned dispersion medium (under the condition of a pressure of 1013.25hPa. The following boiling points are the same) is preferably 100°C~200°C. Among the above-mentioned dispersion media, glycol alkyl ether acetates are preferred because they have a good balance of coating properties, surface tension, etc., and have high solubility of the constituent components of the coloring composition. Moreover, in this case, it is preferable to use a dispersion medium with a boiling point of 150°C or higher. By using a dispersion medium with a high boiling point, it is possible to suppress the rapid drying of the coloring composition from destroying the mutual relationship between the coloring compositions. Furthermore, the dispersion medium having a boiling point of 150° C. or higher may be glycol alkyl ether acetates. The content ratio of the dispersion medium having a boiling point of 150° C. or higher is preferably 3 to 50 mass % in 100 mass % of the entire dispersion medium.

The content of the dispersion medium in the coloring composition can be adjusted appropriately and is not particularly limited. The upper limit of the dispersion medium content in the coloring composition is usually 99% by mass. In addition, considering the viscosity suitable for coating the coloring composition, the lower limit of the dispersion medium content in the coloring composition is usually 70 mass%, preferably 80 mass%. The above-described dispersion medium can be used as a solvent for dissolving and removing precipitates formed from the coloring composition.

(Other admixtures) The coloring composition may be blended with other blending agents in addition to the blending agents within the scope that does not impair the preferred physical properties of the present invention. Examples of other compounding agents include sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, plasticizers, organic carboxylic acid compounds, organic Carboxylic anhydride, pH adjuster, antioxidant, ultraviolet absorber, light stabilizer, preservative, antifungal agent, surfactant, anti-aggregation agent, adhesion improver, development improver, storage stabilizer, etc.

Examples of sensitizing dyes include 4,4'-dimethylaminodiphenylketone, 4,4'-diethylaminodiphenylketone, 2-aminodiphenylketone, and 4-aminodiphenylketone Ketone, 4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone, 3,4-diaminodiphenyl ketone, 2-(p-dimethylaminophenyl )benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzoxazole Methylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)1,3,4-oxazole, 2-(p-dimethylaminophenyl) base) 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) Methylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc.

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

Examples of nonionic surfactants include fluorine-based surfactants, polysiloxane-based surfactants, polyoxyethylene-based surfactants, and the like. Examples of anionic surfactants include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, and alkyl sulfonates. Sulfate ester salts, higher alcohol sulfate ester salts, aliphatic alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether sulfates, Oxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymer surfactants, etc. Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, alkylamine salts, and the like. Examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, and amino acids.

Examples of plasticizers include dioctyl phthalate, di(dodecyl) phthalate, triethylene glycol dioctanoate, dimethyl glycol phthalate, and triphosphate. Toluene, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, etc.

Examples of organic carboxylic acid compounds include monocarboxylic acids, carboxylic acids in which a carboxyl group is directly bonded to a phenyl group, and carboxylic acids in which a carboxyl group is bonded to a phenyl group through a carbon bond.

Examples of organic carboxylic anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, and 1,2- Cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromelite anhydride, naphthalene dicarboxylic anhydride, etc.

>Manufacturing method of coloring composition> The coloring composition can be prepared by mixing a coloring material, a dispersion composition, a binder resin, a dispersion medium, and optionally a cross-linking agent, a photopolymerization initiator, and other blending agents. For example, a mixing and dispersing machine such as a paint stirrer, a bead mill, a ball mill, a dissolver, and a kneader can be used. The coloring composition is preferably filtered after mixing. The coloring composition has alkaline developability and is therefore suitable for use as a color filter.

Furthermore, the coloring material may be surface-treated in advance with the dispersant composition of the present invention. The surface treatment method can be a dry method in which a Henschel mixer, ball mill, atomizer colloid grinder, Bambry mixer, etc. are used to stir the coloring material while adding a dispersant and mix, and then treat it in a solvent and remove the moisture of the solvent. Formula. Surface treatment with the dispersant composition of the present invention as described above can improve the dispersibility of the coloring material and prevent aggregation.

>Color filters> The color filter of the present invention includes a colored layer formed using the aforementioned colored composition.

Examples of the manufacturing method of the color filter include the following methods. First, thermoplastic resin sheets such as polyester resin, polyolefin resin, polycarbonate resin, polymethyl methacrylate resin, etc.; epoxy resin, unsaturated polyester resin, poly(meth)acrylic resin, etc. are thermally cured. Plastic resin sheet; on a transparent substrate such as various glasses, having color pixels that transmit light of the three primary colors of red (R), green (G) and blue (B), preferably a black matrix formed of the aforementioned coloring composition By. As a method of manufacturing a color filter, after applying a black coloring composition, prebaking is performed to evaporate the solvent (dispersion medium) to form a coating film. Then, after exposing the coating film through a photomask, it is developed using an alkaline developer (an aqueous solution containing an organic solvent or surfactant and an alkaline compound, etc.) to dissolve and remove the unexposed parts of the coating film to form a black pattern (black matrix). ). After post-baking if necessary, repeat the same operation in the order of red (R), green (G) and blue (B), thereby obtaining a three-primary color pixel array of red, green and blue on the substrate. Color filters. However, the order of forming pixels of each color in the present invention is not limited to the above.

When coating the coloring composition on the substrate, suitable coating methods such as spray method, roll coating method, spin coating method, slot die coating method, rod coating method, etc. can be used. In particular, spin coating method, slit coating method, etc. are preferably used. Slit die coating method.

After a protective film is formed on the pixel pattern thus obtained if necessary, a transparent conductive film (indium tin oxide (ITO), etc.) is formed by sputtering. After the transparent conductive film is formed, a spacer can be further formed to become a color filter.

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

In addition, since the viscosity of the coloring composition is low and the dispersibility of the coloring material is excellent, it is suitable for use as a coloring column spacer supported on a thin film transistor (TFT) substrate and a color filter sandwiching a liquid crystal layer. piece of substrate. For example, a composition with high optical density (Optical Depth: OD) described in Japanese Patent Application Laid-Open No. 2015-191234 can be cited. [Example]

The present invention will be described in further detail below based on specific embodiments. The present invention is not limited to the following examples, and appropriate modifications can be made without changing the gist of the invention. Furthermore, the polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI) and amine value of the block copolymer and binder resin, the formaldehyde content of the dispersant composition, and the dispersibility of the coloring composition were evaluated according to the following methods. (viscosity, particle size).

Also, the abbreviations are as follows. BMA: butyl methacrylate. PCL5: 5 mol of caprolactone adduct of 2-hydroxyethyl methacrylate (PLACCEL (registered trademark) FM5 manufactured by Daicel Chemical Co., Ltd.). DMAEMA: dimethylaminoethyl methacrylate. DEAEMA: Diethylamine ethyl methacrylate. TBAEMA: tertiary butylaminoethyl methacrylate. BTEE: Ethyl-2-methyl-2-n-butyltelluryl-propionate. DBDT: dibutyl ditelluride. AIBN: 2,2’-Azobis(isobutyronitrile). PMA: propylene glycol monomethyl ether acetate.

(polymerization rate) 1H-NMR (solvent: CDCl3, internal standard: TMS) was measured using a nuclear magnetic resonance (NMR) measurement device (manufactured by Bruker BioSpin, model: AVANCE500 (frequency 500MHz)). From the obtained NMR spectrum, the peak integral ratio of the vinyl group derived from the monomer and the ester side chain derived from the polymer was determined to calculate the polymerization rate of the monomer.

(Weight average molecular weight (Mw) and molecular weight distribution (PDI)) It was determined by gel permeation chromatography (GPC) using high-speed liquid chromatography (HLC-8320 manufactured by TOSOH). The column is one piece of SHODEX KF-603 (φ6mm×150mm) (manufactured by SHODEX Corporation). The mobile phase uses 10mmol/L lithium bromide/10mmol/L acetic acid/N-methyl-2-pyrrolidone solution. The detector uses differential refraction. Plan. The measurement conditions are column temperature 40°C, sample concentration 20 mg/mL, sample injection volume 10 μm, and flow rate 0.2 mL/min. A calibration line (calibration curve) was prepared using polystyrene (molecular weight 427,000, 190,000, 96,400, 37,400, 10,200, 2,630, 906) as a standard material, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured. The molecular weight distribution (PDI=Mw/Mn) was calculated from the measured values.

(amine value) The amine value is expressed by the mass of potassium hydroxide (KOH) equivalent to 1g of alkaline component of the solid content. The measurement sample was dissolved in tetrahydrofuran, and the resulting solution was neutralized and titrated with a 0.1 mol/L hydrochloric acid/2-propanol solution using a potentiometric titration device (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). Taking the inflection point of the titration pH curve as the titration end point, calculate the amine value (B) with the following formula. B=56.11×Vs×0.1×f/w. B: Amine value (mgKOH/g). Vs: The amount of 0.1mol/L hydrochloric acid/2-propanol solution required for titration (mL). f: The price of 0.1mol/L hydrochloric acid (2-propanol). w: Measurement sample mass (g) (solid content conversion).

(viscosity) The viscosity was measured using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Industrial Co., Ltd.) using a conical rotor (1°34'×R24) at 25° C. and a rotor rotation speed of 60 rpm. The colored composition stored at 25° C. for 2 hours after preparation was measured.

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

(amount of formaldehyde) Pour 0.5 g of the dispersant composition into an extraction cartridge (Sep Pak (registered trademark) DNPH Silica Plus Cartridge manufactured by WATERS Co., Ltd. (product number: WAT037500)) and let it stand at room temperature for 2 hours. The extraction cartridge is filled with impregnated DNPH (2, 4-Dinitrophenylhydrazine) in silica gel. Wash out with 4 mL of acetonitrile and dilute to 5 mL in a measuring flask. Use a liquid chromatograph (trade name: LC-10AD manufactured by Shimadzu Corporation, column: Pro C18 RS (4.6 × 250 mm, 5 μm (manufactured by YMC)), mobile phase: acetonitrile/ultrapure water = 65:35 solution, tube Column temperature: 40°C, flow rate: 1.0mL/min, detection wavelength: 360nm), the standard material is measured using two aldehyde-DNPH mixed standard solutions (0.1μg aldehyde/μL acetonitrile, Wako Pure Chemical Industries, Ltd.). Calculated from the measurement results Amount of formaldehyde.

>Manufacturing of block copolymers> (Block copolymer No.1) Add PCL5 (275.8g), BMA (45.3g), AIBN (1.64g), and PMA (80.3g) to a flask equipped with an argon gas inlet tube and a stirrer. After replacing it with argon, add BTEE (14.99g) and DBDT (18.47g). g), react at 60°C for 7 hours. The polymerization rate is 98.3%.

A mixed solution of DEAEMA (191.4g) and PMA (47.9g) previously substituted with argon was added to the obtained solution, and the reaction was carried out at 60°C for 13.5 hours. The polymerization rate is 99.4%.

After the reaction is completed, the reaction solution is poured into stirring n-heptane. The precipitated polymer was vacuum filtered and dried to obtain block copolymer No. 1. The obtained block copolymer No. 1 had an Mw of 16,301, a PDI of 1.44, and an amine value of 108 mgKOH/g. In addition, Table 2 shows the composition of block copolymer No. 1. In addition, the content rate of each structural unit in the copolymer is calculated from the addition ratio of the monomers used in the polymerization reaction and the polymerization rate.

(Block copolymer No.2, 3) Block copolymers No. 2 and 3 were produced in the same manner as the production method of block copolymer No. 1. Table 1 shows the monomers used, organic tellurium compounds, organic ditelluride compounds, azo polymerization initiators, solvents, reaction conditions, and polymerization rates. Table 2 shows the composition, Mw, PDI, and amine value of each block copolymer. In addition, the content rate of each structural unit in the copolymer is calculated from the addition ratio of the monomers used in the polymerization reaction and the polymerization rate.

【Table 1】

>Dispersant composition> 0.325g of each block copolymer was dissolved in 0.675g of PMA to prepare a dispersant composition. The formaldehyde content of the dispersant composition was measured and shown in Table 2.

【Table 2】

In dispersant composition No. 3, the B block of the block copolymer of the dispersant does not have a structural unit of the general formula (1), but has a structural unit derived from dimethylaminoethyl methacrylate (generally In formula (1), R11 and R12 are methyl). The formaldehyde content of dispersant composition No. 3 is 1.7 ppm, which is relatively high. On the other hand, in dispersant composition Nos. 1 and 2, the B block of the block copolymer of the dispersant has a structural unit of the general formula (1). The formaldehyde amounts of these dispersant composition Nos. 1 and 2 are 0.1 ppm and 0.0 ppm, which are very low.

>Synthesis of alkali-soluble resin (binder resin)> Add methacrylic acid (MAA) (40.0g), benzyl methacrylate (BzMA) (160.0g), and propylene glycol monomethyl ether acetate (PMA) (580.0g) to a flask equipped with an argon gas introduction tube and a stirrer. ), substituted with argon, added 2,2'-azobis(isobutyronitrile) (AIBN) (4.0g), n-dodecanethiol (6.0g), and PMA (20.0g), and raised the temperature to 90°C. While maintaining the solution at 90°C, MAA (80.0g), BzMA (320.0g), AIBN (8.0g), n-dodecanethiol (12.0g), and PMA (50.0) were added dropwise to the solution over 1.5 hours. g). 60 minutes after the completion of the dropwise addition, the temperature was raised to 110°C, AIBN (0.8g) and PMA (10.0g) were added and reacted for 1 hour, and AIBN (0.8g) and PMA (10.0g) were further added and reacted for 1 hour. AIBN (0.8g) and PMA (10.0g) were further added and reacted for 1 hour.

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

>Preparation of coloring compositions> Coloring composition No.1 Prepare a blending composition of 8 parts by mass of pigment, 6 parts by mass of block copolymer No. 1, 6 parts by mass of alkali-soluble resin, and 80 parts by mass of PMA, add 555 parts by mass of 0.3mm zirconium dioxide beads, and use a bead mill to (Trade name: DISPERMAT CA, manufactured by VMA-GETZMANN GmbH) Mix for 3 hours and disperse thoroughly. After the dispersion is completed, the beads are filtered to obtain a colored composition. C.I. Pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals) was used as the pigment. The dispersibility of the obtained colored composition was evaluated. The evaluation results are shown in Table 3.

Coloring composition No.2, 3 Coloring compositions No. 2 and 3 were prepared in the same manner as the preparation method of coloring composition No. 1, except that the block copolymer was changed. The evaluation results are shown in Table 3.

【table 3】

Coloring composition Nos. 1 to 3 all have good pigment dispersibility. Therefore, it can be understood that a block copolymer in which the B block has a structural unit of the general formula (1) can be used as a dispersant. Moreover, in particular, Colored Composition No. 1 is excellent in pigment dispersibility and uses a block copolymer in which the B block has a structural unit derived from diethylaminoethyl methacrylate. Therefore, it was found that when a block copolymer in which the B block has a structural unit derived from diethylaminoethyl methacrylate is used, a colored composition with reduced formaldehyde content and excellent pigment dispersibility can be obtained.

The present invention includes the following embodiments. (Embodiment 1) A dispersant composition containing a polymer having a structure represented by the general formula (5) in a side chain. *-Y ¹ -NR ¹¹ R ¹² (5) [In the general formula (5), R ¹¹ represents a hydrogen atom and a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure. Y ¹ represents a divalent hydrocarbon group. *Indicates bonding. ]

(Implementation 2) The dispersant composition as described in aspect 1, wherein the amine value of the aforementioned polymer is 10 mgKOH/g~200 mgKOH/g.

(Implementation pattern 3) The dispersant composition according to aspect 1 or 2, wherein the polymer is a block copolymer having an A block and a B block, and the A block has a (meth)acrylic acid group-derived monomer. Structural unit, the aforementioned B block has a structural unit represented by general formula (1).

[Chemical formula 8] [In the general formula (1), R ¹¹ represents a hydrogen atom and a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure. R ¹³ represents a hydrogen atom or a methyl group. X ¹ represents a amide group, an ester group, or a single bond. Y ¹ represents a divalent hydrocarbon group. ]

(Implementation pattern 4) The dispersant composition according to aspect 3, wherein the A block has a structural unit represented by general formula (10).

[Chemical formula 9] [In general formula (10), n1 represents an integer from 1 to 10. R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 1 to 10 carbon atoms. R ³ represents an alkylene group having 1 to 10 carbon atoms. ]

(Implementation pattern 5) The dispersant composition according to aspect 3 or 4, wherein the molecular weight distribution (PDI) of the block copolymer is 2.5 or less.

(Implementation pattern 6) The dispersant composition according to any one of aspects 3 to 5, wherein the block copolymer is polymerized by living radical polymerization.

(Implementation pattern 7) A colored composition containing the dispersant composition described in any one of aspects 1 to 6, a coloring material, a binder resin and a dispersion medium.

(Implementation pattern 8) The colored composition described in aspect 7 is used for color filters.

(Implementation pattern 9) A color filter having a colored layer formed using the colored composition described in aspect 8.

Claims (9)

A dispersant composition comprising a block copolymer having an A block and a B block, wherein the aforementioned A block has a structural unit represented by the general formula (10), and the aforementioned B block has a structure represented by the general formula (1) unit,

In the general formula (10), n1 represents an integer from 1 to 10, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group with a carbon number of 1 to 10, and R ³ represents an alkylene group with a carbon number of 1 to 10. base,

In the general formula (1), R ¹¹ represents a hydrogen atom and a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, and R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. Hydrocarbon group, R ¹¹ and R ¹² can bond with each other to form a cyclic structure, R ¹³ represents a hydrogen atom or a methyl group, X ¹ represents a amide group, an ester group, or a single bond, Y ¹ represents a divalent hydrocarbon group, where the aforementioned A is embedded The segment further includes (meth)acrylate having a chain alkyl group, (meth)acrylate having a cyclic alkyl group, (meth)acrylate having a polycyclic structure, and having an aromatic group. (Meth)acrylate, (meth)acrylate having a polyalkylene glycol structural unit, (meth)acrylate having a hydroxyl group, (meth)acrylate having an alkoxy group, having an oxygen-containing heterocyclic group One or more structural units in the (meth)acrylate, the aforementioned A block does not contain the structural unit represented by the general formula (1), or contains less than 10 mass percent of the general formula (1) Among the structural units shown, the B block contains substantially no structural unit derived from a vinyl monomer having an acidic group. The dispersant composition according to claim 1, wherein the amine value of the aforementioned block copolymer is 10 mgKOH/g~200 mgKOH/g. The dispersant composition according to claim 1, wherein the A block does not contain the structural unit represented by the general formula (1). The dispersant composition according to claim 1, wherein the dispersant component contains only the above-mentioned block copolymer, or only contains a polymerization product containing the above-mentioned block copolymer. The dispersant composition according to claim 1, wherein the molecular weight distribution (PDI) of the aforementioned block copolymer is 2.5 or less. The dispersant composition according to any one of claims 1 to 5, wherein the block copolymer is polymerized by living radical polymerization. A colored composition containing the dispersant composition as described in any one of claims 1 to 6, a coloring material, a binder resin and a dispersion medium. The colored composition according to claim 7, which is used for color filters. A color filter having a colored layer formed using the colored composition described in claim 8.