Block copolymer, dispersant, and coloring composition

Abstract

[Problem] To provide a block copolymer that has ultraviolet curability and that exhibits high colorant dispersing ability when used as a dispersant in a coloring composition. [Solution] An ABC-type triblock copolymer comprising blocks A-C respectively formed through radical polymerization of polymerizable compositions (A)-(C), wherein: the polymerizable composition (A) contains a (meth)acrylate having a hydroxy group and / or a (meth)acrylate having an alkoxy group; the polymerizable composition (B) contains a vinyl monomer (b-1) having a nitrogen-containing functional group; the polymerizable composition (C) contains a vinyl monomer (c-1) having a (meth)acryloyl group and an ethylenically unsaturated group; and the molar volume ratio (X / Y) of a structural unit (X) that is derived from the monomer (c-1) and that has an ethylenically unsaturated group with respect to a structural unit (Y) derived from the vinyl monomer (b-1) is 0.1-1.1.

Description

Block copolymer, dispersant, and colored composition

[0001] The present invention relates to block copolymers, and more particularly to block copolymers that can be used as dispersants for colorants in colored compositions.

[0002] Conventionally, in the manufacture of color filters used in liquid crystal displays and the like, methods for applying colorants to substrates include dyeing, printing, inkjet, electrodeposition, and pigment dispersion. Among these, pigment dispersion has become the mainstream method from the viewpoint of spectral characteristics, durability, pattern shape, and accuracy. In this pigment dispersion method, a coating film consisting of a colored composition mixed with pigment, dispersant, dispersion medium, binder resin, etc., is formed on a substrate, cured by irradiation with radiation through a photomask with a desired pattern shape, and then alkaline development is performed.

[0003] In recent years, increasing the concentration of pigments in coloring compositions has been investigated to obtain good color reproduction and high contrast in color filters. When the pigment concentration is increased, the proportion of dispersant decreases relatively, so the dispersant needs to have high dispersibility (see, for example, Patent Document 1 (paragraph 0004)). In addition, in alkaline development, alkali-soluble binder resins play a major role.

[0004] However, in the case of colored compositions with high pigment concentrations, the proportion of binder resin, which is a developing component, decreases, and the alkali developability deteriorates. Therefore, there is a need for a dispersant that can improve the alkali developability of colored compositions. As such a dispersant, a block copolymer consisting of a solvent affinity block having a hydroxyl group and / or alkoxy group and a colorant affinity block having a nitrogen-containing functional group is used (see Patent Document 2 (paragraphs 0243, 0244) and Patent Document 3 (claim 1)).

[0005] On the other hand, in the manufacture of color filters, shortening the UV irradiation time to reduce costs can lead to poor curing of the coloring composition. When a poorly cured coating is alkaline developed, a color difference occurs due to the difference in thickness between the fully cured and insufficiently cured areas. Furthermore, if the coating is not sufficiently cured, its resistance to solvents is poor, making it unreliable. Therefore, it has been proposed to use a resin-type dispersant having a (meth)acryloyl group (see Patent Document 4 (Claim 1)).

[0006] Japanese Patent Publication No. 2009-265515, Japanese Patent Publication No. 2009-52010, Japanese Patent Publication No. 2013-119568, Japanese Patent Publication No. 2021-85955

[0007] Conventionally, when introducing double bonds into block copolymers used as dispersants, a block copolymer without double bonds in its side chains but with reactive groups in its side chains is synthesized first, and then a compound with double bonds is reacted with the reactive groups in a post-reaction to introduce the double bonds. However, structural units into which double bonds are introduced in this way tend to have a larger molar volume, which promotes the desorption of adsorption sites from colorants when used as a dispersant, and tends to reduce the dispersion performance of colorants. The present invention has been made in view of the above circumstances, and aims to provide a block copolymer that is UV curable and has high dispersion performance of colorants when used as a dispersant for colored compositions.

[0008] The block copolymer of the present invention, which has been able to solve the above problems, is an ABC-type triblock copolymer having A block, B block and C block, wherein A block, B block and C block are formed by radical polymerization of polymerizable composition (A), polymerizable composition (B), or polymerizable composition (C), respectively, wherein polymerizable composition (A) contains a (meth)acrylate (a-1) having a hydroxyl group and / or a (meth)acrylate (a-2) having an alkoxy group, and polymerizable composition (B) contains The polymerizable composition (C) contains a vinyl monomer (b-1) having a nitrogen functional group, and the polymerizable composition (C) contains a vinyl monomer (c-1) having a (meth)acryloyl group and an ethylenically unsaturated group other than the (meth)acryloyl group in one molecule, wherein the vinyl monomer (c-1) is characterized in that the molar volume ratio (X / Y) of a structural unit (X) derived from the vinyl monomer (c-1) and having an ethylenically unsaturated group other than the (meth)acryloyl group to a structural unit (Y) derived from the vinyl monomer (b-1) is 0.1 to 1.1.

[0009] The block copolymer exhibits an effect of enhancing the dispersibility of colorants because block A has appropriate compatibility with the dispersion medium and block B has high adsorption to colorants. Furthermore, the block copolymer has curability because block C contains structural unit (X). Moreover, since the molar volume ratio (X / Y) of structural unit (X) to structural unit (Y) is 0.1 to 1.1, when used as a dispersant, the desorption of adsorption sites from the colorant is suppressed, and ethylenically unsaturated groups can be introduced while suppressing a decrease in the dispersion performance of the colorant. Therefore, by using the block copolymer of the present invention as a dispersant for a colored composition, the dispersion performance of the colorant can be improved and the curability of the colored composition can be enhanced.

[0010] The block copolymer of the present invention is UV-curable and exhibits high dispersion performance of colorants when used as a dispersant for colored compositions.

[0011] The following describes an example of a preferred embodiment of the present invention. However, the following embodiments are merely illustrative. The present invention is not limited in any way to the following embodiments.

[0012] <Definitions> In this specification, "(meth)acrylic" means "at least one of acrylic and methacrylic." "(meth)acrylate" means "at least one of acrylate and methacrylate," and is also an ester compound in which the hydrogen atom of the carboxyl group of (meth)acrylic acid is replaced with an organic group. "(meth)acryloyl" means "at least one of acryloyl and methacryloyl." "(meth)acrylic monomer" means "a monomer having a (meth)acryloyl group in its molecule," and also includes "(meth)acrylate." "Vinyl monomer" means "a monomer having a radically polymerizable carbon-carbon double bond in its molecule," and also includes "(meth)acrylate" and "(meth)acrylic monomer."

[0013] In this specification, "structural unit derived from (meth)acrylate" means "a structural unit in which the radically polymerizable carbon-carbon double bond of (meth)acrylate polymerizes to form a carbon-carbon single bond." "Structural unit derived from (meth)acrylic monomer" means "a structural unit in which the radically polymerizable carbon-carbon double bond of (meth)acrylic monomer polymerizes to form a carbon-carbon single bond." "Structural unit derived from vinyl monomer" means "a structural unit in which the radically polymerizable carbon-carbon double bond of vinyl monomer polymerizes to form a carbon-carbon single bond."

[0014] In this specification, "X to Y" (where X and Y are any numbers) means "greater than or equal to X and less than or equal to Y". Furthermore, "greater than or equal to X" (where X is any number) also includes "X or greater than X", and "less than or equal to Y" (where Y is any number) also includes "Y or less than Y". In addition, "X and / or Y (where X and Y are any combination)" means "at least one of X and Y", and has three possible combinations: "X only", "Y only", and "X and Y".

[0015] <Block Copolymer> The block copolymer of the present invention is an ABC-type triblock copolymer containing A block, B block, and C block. In this specification, "A block" can be replaced with "A segment," "B block" can be replaced with "B segment," and "C block" can be replaced with "C segment."

[0016] (Block A) The Block A is formed by radical polymerization of the polymerizable composition (A) for Block A, and is a polymer of the polymerizable composition (A).

[0017] (Hydroxy group-containing (meth)acrylate (a-1) and / or alkoxy group-containing (meth)acrylate (a-2)) The polymerizable composition (A) contains a hydroxy group-containing (meth)acrylate (a-1) and / or alkoxy group-containing (meth)acrylate (a-2). By having structural units derived from these hydroxy group-containing (meth)acrylate (a-1) and / or alkoxy group-containing (meth)acrylate (a-2), block A can have compatibility with the dispersion medium while improving the alkali developability of the colored composition. The (meth)acrylate (a-1) and (meth)acrylate (a-2) may be used individually or in combination of two or more.

[0018] The total content of (meth)acrylate (a-1) and (meth)acrylate (a-2) in 100 mol% of monomer contained in the polymerizable composition (A) is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. When the total content ((a-1) + (a-2)) is within the above range, the alkali developability of the colored composition is further improved while maintaining compatibility with the dispersion medium.

[0019] Examples of the (meth)acrylic monomer (a-1) having a hydroxyl group include (meth)acrylate having a hydroxyalkyl group, (meth)acrylate having a lactone-modified hydroxyl group, and (meth)acrylate having a hydroxypolyalkylene glycol group.

[0020] The hydroxyalkyl group of the (meth)acrylate having the hydroxyalkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Furthermore, the hydroxyalkyl group is preferably linear or branched. Specific examples of the (meth)acrylate having the hydroxyalkyl group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate.

[0021] Examples of the lactone-modified hydroxyl group-containing (meth)acrylate include those obtained by adding a lactone to a (meth)acrylate having a hydroxyalkyl group, with caprolactone being preferred. The amount of caprolactone added is preferably 1 mol to 20 mol, more preferably 1 mol to 10 mol. Specific examples of the lactone-modified hydroxyl group-containing (meth)acrylate include a 1 mol adduct of caprolactone to 2-hydroxyethyl (meth)acrylate, a 2 mol adduct of caprolactone to 2-hydroxyethyl (meth)acrylate, a 3 mol adduct of caprolactone to 2-hydroxyethyl (meth)acrylate, a 4 mol adduct of caprolactone to 2-hydroxyethyl (meth)acrylate, a 5 mol adduct of caprolactone to 2-hydroxyethyl (meth)acrylate, and a 10 mol adduct of caprolactone to 2-hydroxyethyl (meth)acrylate. Examples of (meth)acrylates having hydroxypolyalkylene glycol groups include terminal hydroxyl group polyethylene glycol (degree of polymerization = 2 to 30) mono(meth)acrylate and terminal hydroxyl group polypropylene glycol (degree of polymerization = 2 to 30) mono(meth)acrylate.

[0022] As the (meth)acrylate (a-1) having a hydroxyl group, the monomer represented by formula (1) is preferred. The structural unit derived from the monomer represented by formula (1) has an ester bond portion in the side chain and a hydroxyl group at the end of the side chain, and is therefore expected to have a high affinity with the dispersion medium and binder resin, thereby further improving the dispersibility and alkali developability of the colored composition using the block copolymer.

[0023] [In equation (1), m1 represents an integer from 0 to 10. R 11 R represents a hydrogen atom or a methyl group. 12 R represents an alkylene group with 1 to 10 carbon atoms. 13 R represents an alkylene group with 1 to 10 carbon atoms. Note that if m1 is 2 or more, there are multiple R groups. 13 These may be the same or different.

[0024] In formula (1), m1 is preferably an integer of 1 to 7, more preferably an integer of 1 to 5. R 12 The alkylene group represented by R 12 may be linear or branched, but a linear one is preferred. Specific examples of the alkylene group represented by R 12 include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, a 1-methylethylene group, and the like. The alkylene group represented by R

[0025] R 13 The alkylene group represented by may be linear or branched, but a linear one is preferred. R 13 Specific examples of the alkylene group represented by include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, and the like. R 13 The alkylene group represented by is preferably 1 to 8 carbon atoms, more preferably 3 to 8 carbon atoms.

[0026] When the polymerizable composition (A) contains a (meth)acrylate (a-1) having a hydroxy group, the content of the (meth)acrylate (a-1) in 100 mol% of the monomers contained in the polymerizable composition (A) is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less. When the content of the (meth)acrylate (a-1) is within the above range, the compatibility with the dispersion medium is maintained while the alkali developability of the coloring composition is further improved.

[0027] Examples of the (meth)acrylate (a-2) having an alkoxy group include (meth)acrylates having an alkoxyalkyl group and (meth)acrylates having an alkoxypolyalkylene glycol group.

[0028] Examples of (meth)acrylates having the aforementioned alkoxyalkyl group include methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate.

[0029] Examples of (meth)acrylates having alkoxypolyalkylene glycol groups include polyethylene glycol (degree of polymerization = 2-30) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization = 2-30) ethyl ether (meth)acrylate, polyethylene glycol (degree of polymerization = 2-30) propyl ether (meth)acrylate, and other (meth)acrylates having alkoxypolypropylene glycol groups, such as polypropylene glycol (degree of polymerization = 2-30) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization = 2-30) ethyl ether (meth)acrylate, and polypropylene glycol (degree of polymerization = 2-30) propyl ether (meth)acrylate.

[0030] As the (meth)acrylate (a-2) having an alkoxy group, the monomer represented by formula (2) is preferred. Since the structural unit derived from the monomer represented by formula (2) has an ether bond portion and a terminal alkoxy group in its side chain, it has high affinity with the dispersion medium and binder resin, and the resolubility of the colored composition using the block copolymer in the dispersion medium is further improved.

[0031] [In equation (2), m² represents an integer between 2 and 30. R 21 R represents a hydrogen atom or a methyl group. 22 R represents an alkylene group with 1 to 3 carbon atoms. 23 R represents an alkylene group with 1 to 3 carbon atoms. Note that there are multiple R groups. 23 These may be the same or different. 24 This represents an alkyl group with 1 to 3 carbon atoms.

[0032] In formula (2), m2 is 2 or more, preferably 5 or more, and 30 or less, preferably 20 or less, and even more preferably 15 or less. 22 , R23 The alkylene group having 1 to 3 carbon atoms, as indicated by R, may be linear or branched, but linear is preferred. 22 The alkylene group having 1 to 3 carbon atoms as indicated by is preferably an ethylene group or a trimethylene group. 23 The alkylene group having 1 to 3 carbon atoms as indicated by is preferably an ethylene group or a trimethylene group. 24 The alkyl group having 1 to 3 carbon atoms, as shown, may be linear or branched, but linear is preferred. 24 Specific examples of alkyl groups having 1 to 3 carbon atoms, as shown, include the methyl group, ethyl group, n-propyl group, and isopropyl group.

[0033] When the polymerizable composition (A) contains a (meth)acrylate (a-2) having an alkoxy group, the content of the (meth)acrylate (a-2) in 100 mol% of the monomer contained in the polymerizable composition (A) is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. If the content of the (meth)acrylate (a-2) is within the above range, the alkali developability of the colored composition is further improved while maintaining compatibility with the dispersion medium.

[0034] The polymerizable composition (A) preferably contains a (meth)acrylate (a-1) having a hydroxyl group, more preferably contains a (meth)acrylate having a hydroxyalkyl group and / or a (meth)acrylate having a lactone-modified hydroxyl group, and even more preferably contains a (meth)acrylate having a lactone-modified hydroxyl group.

[0035] ((meth)acrylate(a-3)) The polymerizable composition (A) may contain (meth)acrylate(a-3) represented by formula (3). The (meth)acrylate(a-3) represented by formula (3) may be used alone or in combination of two or more types.

[0036] [In equation (3), R 31 R represents a hydrogen atom or a methyl group. 32 This represents a linear alkyl group or a cyclic alkyl group.

[0037] R 32 The linear alkyl groups represented by include linear alkyl groups and branched alkyl groups. For linear alkyl groups, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-nonyl, n-decyl, and n-lauryl groups. For branched alkyl groups, the number of carbon atoms is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5. Examples of branched alkyl groups include isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, neopentyl, and isooctyl groups.

[0038] R 32 Examples of cyclic alkyl groups represented by include cyclic alkyl groups having a monocyclic structure and cyclic alkyl groups having a crosslinked ring structure, each of which may have a chain-like portion. The number of carbon atoms in the cyclic alkyl group is preferably 4 to 18, more preferably 5 to 12, and even more preferably 6 to 10. Examples of cyclic alkyl groups having a monocyclic structure include cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. Examples of cyclic alkyl groups having a crosslinked ring structure include bornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, norbornyl group, and dicyclopentanyl group.

[0039] Specific examples of (meth)acrylates having the linear alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate. Specific examples of (meth)acrylates having the branched alkyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, and isodecyl (meth)acrylate.

[0040] Specific examples of (meth)acrylates having a monocyclic cyclic alkyl group include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, and cyclododecyl (meth)acrylate. Specific examples of (meth)acrylates having a cyclic alkyl group with a cross-linked ring structure include isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate.

[0041] The (meth)acrylate (a-3) represented by formula (3) is preferably a (meth)acrylate having a linear alkyl group (straight-chain alkyl group or branched-chain alkyl group).

[0042] When the polymerizable composition (A) contains (meth)acrylate (a-3) represented by formula (3), the content of (meth)acrylate (a-3) in 100 mol% of monomer contained in the polymerizable composition (A) is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 80 mol% or less. If the content of (meth)acrylate (a-3) is within the above range, the compatibility with the dispersion medium is further improved.

[0043] If the polymerizable composition (A) contains (meth)acrylate (a-3) represented by formula (3), the total content of (meth)acrylate (a-1), (meth)acrylate (a-2), and (meth)acrylate (a-3) in 100 mol% of the monomer contained in the polymerizable composition (A) ((a-1) + (a-2) + (a-3)) is preferably 70 mol% or more, more preferably 85 mol% or more, and even more preferably 95 mol% or more. If the total content ((a-1) + (a-2) + (a-3)) is within the above range, the affinity of block A to the dispersion medium can be further increased. Note that the polymerizable composition (A) may contain only the vinyl monomers (a-1), (a-2), and (a-3) as monomers.

[0044] The polymerizable composition (A) may contain other monomers other than (meth)acrylate (a-1), (meth)acrylate (a-2), and (meth)acrylate (a-3) to an extent that does not impair the effects of the present invention.

[0045] Other monomers that may be contained in the polymerizable composition (A) include (meth)acrylic monomers and vinyl monomers other than (meth)acrylic monomers. The other monomers may consist of only one type or two or more types.

[0046] Examples of the (meth)acrylic monomer include (meth)acrylic monomers having an aryl group, (meth)acrylic monomers having an oxygen-containing heterocyclic group, (meth)acrylic monomers having an amide group, and (meth)acrylic monomers having an acidic group.

[0047] The aryl group of the (meth)acrylic monomer having the aryl group preferably has 6 to 12 carbon atoms and may have a chain-like portion such as an alkylaryl group, aralkyl group, or aryloxyalkyl group. Specific examples of the (meth)acrylate having the aryl group include benzyl (meth)acrylate, phenyl (meth)acrylate, and phenoxyethyl (meth)acrylate.

[0048] The oxygen-containing heterocyclic group of the (meth)acrylic monomer having the oxygen-containing heterocyclic group is preferably a 4-membered to 6-membered ring. Specific examples of the (meth)acrylic monomer having the oxygen-containing heterocyclic group include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropaneformal (meth)acrylate, and 2-[(2-tetrahydropyranyl)oxy]ethyl (meth)acrylate.

[0049] Examples of (meth)acrylic monomers having the amide group include N,N-dimethyl(meth)acrylamide and 4-(meth)acryloylmorpholin.

[0050] Examples of acidic groups found in the (meth)acrylic monomer having the aforementioned acidic group include a carboxyl group (-COOH), a sulfonic acid group (-SO3H), a phosphate group (-OPO3H2), a phosphonic acid group (-PO3H2), and a phosphinic acid group (-PO2H2). Specific examples of the (meth)acrylic monomer having the acidic group include (meth)acrylic acid; (meth)acrylates having a carboxyl group such as 2-(meth)acryloyloxy)ethyl hydrogen succinate, 2-(meth)acryloyloxy)ethyl hydrogen hexahydrophthalate, 2-(meth)acryloyloxy)ethyl hydrogen phthalate, caprolactone adduct of (meth)acrylic acid, 2-carboxyethyl (meth)acrylic acid, 2-carboxypropyl (meth)acrylic acid, 3-carboxypropyl (meth)acrylic acid, 4-carboxybutyl (meth)acrylic acid, and 5-carboxypentyl (meth)acrylic acid; (meth)acrylates having a phosphate group such as 2-(phosphonooxy)ethyl (meth)acrylic acid; and (meth)acrylates having a sulfonic acid group such as 2-sulfoethyl (meth)acrylic acid and 2-(meth)acrylamido-2-methylpropanesulfone. Preferably, (meth)acrylic acid and (meth)acrylates having a carboxyl group are used.

[0051] The vinyl monomer other than the (meth)acrylic monomer is not particularly limited as long as it is formed from a vinyl monomer that can copolymerize with the (meth)acrylic monomer. Examples of vinyl monomers other than the (meth)acrylic monomer include α-olefins, styrene monomers, vinyl monomers having a hydroxyl group, vinyl monomers having a heterocycle, vinyl amides, vinyl carboxylates, dienes, etc. Examples of the α-olefin include 1-hexene, 1-octene, 1-decene, etc. Examples of the styrene monomer include substituted or unsubstituted styrene. Examples of substituents that may be substituted on styrene include alkyl groups, aryl groups, alkoxy groups, aryloxy groups, etc. Furthermore, styrene monomers also include fused ring compounds in which two or more benzene rings are fused. Specific examples of the styrene monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 2,4-dimethylstyrene, 4-methoxystyrene, 4-phenylstyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene, etc. Examples of vinyl monomers having a hydroxyl group include 4-vinylphenol, 4-hydroxybutyl vinyl ether, etc. Examples of the heterocyclic vinyl monomers include 2-vinylthiophene, N-methyl-2-vinylpyrrole, and 1-vinyl-2-pyrrolidone. Examples of the vinylamides include N-vinylformamide, N-vinylacetamide, and N-vinyl-ε-caprolactam. Examples of the vinyl carboxylates include vinyl acetate, vinyl pivalate, and vinyl benzoate. Examples of the dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, and 7-methyl-1,6-octadiene.

[0052] The polymerizable composition (A) contains (meth)acrylic monomer in 100 mol% of monomer, preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more. The polymerizable composition (A) may contain only (meth)acrylic monomer as the monomer.

[0053] The polymerizable composition (A) preferably contains substantially no vinyl monomer (b-1) having a nitrogen-containing functional group, as described later. The content of vinyl monomer (b-1) in 100 mol% of monomer in the polymerizable composition (A) is preferably 3 mol% or less, more preferably 2 mol% or less, and even more preferably 1 mol% or less.

[0054] Preferably, the polymerizable composition (A) does not substantially contain vinyl monomer (c-1) having an (meth)acryloyl group and an ethylenically unsaturated group other than the (meth)acryloyl group in one molecule, as described later. The content of vinyl monomer (c-1) in 100 mol% of monomer in the polymerizable composition (A) is preferably 3 mol% or less, more preferably 2 mol% or less, and even more preferably 1 mol% or less.

[0055] The various structural units contained in Block A may be contained in Block A in any manner, such as random copolymerization or block copolymerization, and it is preferable that they be contained in a manner of random copolymerization from the viewpoint of uniformity. For example, Block A may be formed by a copolymer of structural units consisting of Block a1 and structural units consisting of Block a2.

[0056] (Block B) The Block B is formed by radical polymerization of the polymerizable composition (B) for Block B, and is a polymer of the polymerizable composition (B).

[0057] (Vinyl monomer (b-1)) The polymerizable composition (B) contains a vinyl monomer (b-1) having a nitrogen-containing functional group. The B block has structural units derived from the vinyl monomer (b-1) having a nitrogen-containing functional group, and therefore has high adsorption properties to colorants. The vinyl monomer (b-1) may be used alone or two or more may be used in combination.

[0058] Examples of nitrogen-containing functional groups include amino groups, nitrogen-containing heterocyclic groups, amide groups, cyano groups, etc., with amino groups or nitrogen-containing heterocyclic groups being preferred among these. In this specification, the amino group refers to a general amino group (-NH2), as well as a group in which H is substituted with a hydrocarbon group, -NH2 a , -NR a R b (R a , R b Each of these independently represents a chain-like or cyclic hydrocarbon group. Also, R a and R b The groups may be bonded to each other to form a cyclic structure. This includes substituted amino groups represented by ). Examples of nitrogen-containing heterocyclic groups include aromatic heterocyclic groups such as 4-pyridyl group, 1-imidazole group, 2-pyridyl group, 9-carbazole group, and phthalimide group; and non-aromatic heterocyclic groups such as 1-piperidyl group, 4-morpholino group, 1-pyrrolidyl group, pyrrolidone group, methylpyrrolidone group, ethylpyrrolidone group, propylpyrrolidone group, and butylpyrrolidone group.

[0059] The nitrogen-containing functional group of the vinyl monomer (b-1) is preferably basic. In other words, the vinyl monomer (b-1) having a nitrogen-containing functional group is preferably a vinyl monomer having a basic group. The basic group is a group that exhibits basicity, and is more preferably an amino group due to the availability of raw materials and ease of synthesis. Therefore, the vinyl monomer (b-1) having a nitrogen-containing functional group is more preferably a vinyl monomer having an amino group.

[0060] The vinyl monomer (b-1) having a nitrogen-containing functional group is preferably a vinyl monomer represented by formula (4).

[0061] [In equation (4), R 41 represents a hydrogen atom or a methyl group. A 41 R represents a single bond or a divalent linking group. 42 and R 43 Each of these independently represents a hydrocarbon group that may contain heteroatoms. 42 and R 43These may be joined together to form a ring structure.

[0062] A 41 The divalent linking groups represented by include linear alkylene groups having 1 to 10 carbon atoms, branched alkylene groups having 3 to 10 carbon atoms, cyclic alkylene groups having 3 to 12 carbon atoms, arenediyl groups having 6 to 12 carbon atoms, and ester groups (-CO-O-R). 411 -), amide group (-CO-NH-R 412 Examples include -). The bonding direction of the ester group and amide group is not particularly limited, but the bonding configuration of the ester group is C-CO-O-R. 411 -N is preferred, and the bonding configuration of the amide group is C-CO-NH-R 412 -N is preferred.

[0063] The linear alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples include a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, etc. The branched alkylene group preferably has 3 to 10 carbon atoms, and examples include a propylene group, propyridene group, 1,2-butanediyl group, 1,3-butanediyl group, etc. The cyclic alkylene group may have a chain portion, preferably 3 to 12 carbon atoms, more preferably 5 to 12 carbon atoms, and examples include a cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, etc. The arenediyl group may have a chain portion, preferably 6 to 12 carbon atoms, and examples include a phenylene group, etc. A 41 The linking group is preferably a divalent group, and more preferably an ester group or an amide group from the viewpoint of affinity with the dispersion medium and binder resin. 411 and R 412 Examples include linear alkylene groups having 1 to 10 carbon atoms, branched alkylene groups having 3 to 10 carbon atoms, cyclic alkylene groups having 3 to 12 carbon atoms, and arenediyl groups having 6 to 12 carbon atoms, with linear alkylene groups having 1 to 10 carbon atoms being preferred.

[0064] R 42 and R 43Hydrocarbon groups that may contain heteroatoms represented by include linear hydrocarbon groups and cyclic hydrocarbon groups, with linear hydrocarbon groups being preferred. A hydrocarbon group containing a heteroatom has a structure in which carbon atoms in the hydrocarbon group are replaced by heteroatoms. Examples of heteroatoms that the hydrocarbon group may contain include oxygen atoms. Examples of linear hydrocarbon groups include linear alkyl groups and branched alkyl groups, with linear alkyl groups being preferred. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms, such as methyl groups, ethyl groups, n-propyl groups, and n-butyl groups. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms, such as isopropyl groups, isobutyl groups, sec-butyl groups, and tert-butyl groups. Examples of cyclic hydrocarbon groups include cyclic alkyl groups and aromatic groups. The cyclic alkyl group may have a chain-like portion, preferably having 3 to 18 carbon atoms, more preferably 5 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples include cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. The aromatic group may have a chain-like portion, preferably having 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms. Examples include phenyl group, tolyl group, xylyl group, and mesityl group.

[0065] R 42 and R 43 The fact that they are bonded to each other to form a ring structure means that R 42 and R 43 This refers to the formation of a cyclic structure via a nitrogen atom. Examples of such cyclic structures include nitrogen-containing heterocycles with 5 to 7 members or fused rings formed by the fusion of two such heterocycles. Specifically, examples include structures represented by the following formulas (4-1), (4-2), and (4-3).

[0066] [In equations (4-1), (4-2), and (4-3), R 44* represents an alkyl group with 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. * represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, there are multiple R groups. 44 These may be the same or different.

[0067] Specific examples of vinyl monomers represented by formula (4) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, ethylaminoethyl (meth)acrylate, ethylaminopropyl (meth)acrylate, ethylaminobutyl (meth)acrylate, propylaminoethyl (meth)acrylate, propylaminopropyl (meth)acrylate, propylaminobutyl (meth)acrylate, dimethylaminopropyl (meth)acrylamide, and the like.

[0068] The content of vinyl monomer (b-1) in 100 mol% of the monomer contained in the polymerizable composition (B) is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more. If the content of vinyl monomer (b-1) is within the above range, the adsorption of block B to the coloring agent can be further enhanced.

[0069] The polymerizable composition (B) may contain other monomers other than the vinyl monomer (b-1) to an extent that does not impair the effects of the present invention. Specific examples of monomers that the polymerizable composition (B) may contain include those exemplified as specific examples of monomers contained in the polymerizable composition (A), as well as vinyl monomers having a salt of a basic group, (meth)acrylic monomers having a chain alkyl group, (meth)acrylic monomers having a cyclic alkyl group, (meth)acrylic monomers having an aryl group, (meth)acrylic monomers having a hydroxyalkyl group, and the like.

[0070] Examples of basic groups in vinyl monomers having a salt of the basic group include amino groups. Examples of salts of basic groups include halogenated salts of basic groups (F, Cl, Br, I, etc.), inorganic salts such as sulfates, and sulfonates, sulfates, phosphates, or carboxylates of organic compounds. Examples of (meth)acrylic monomers having a chain alkyl group, a cyclic alkyl group, an aryl group, and a hydroxyalkyl group include those exemplified as monomers contained in polymerizable composition (A).

[0071] Preferably, the polymerizable composition (B) does not substantially contain vinyl monomer (c-1) having an (meth)acryloyl group and an ethylenically unsaturated group other than the (meth)acryloyl group in one molecule, as described later. The content of vinyl monomer (c-1) in 100 mol% of monomer in the polymerizable composition (B) is preferably 3 mol% or less, more preferably 2 mol% or less, and even more preferably 1 mol% or less.

[0072] The various structural units contained in the B block may be contained in the B block in any manner, such as random copolymerization or block copolymerization, and it is preferable that they be contained in a manner of random copolymerization from the viewpoint of uniformity. For example, the B block may be formed by a copolymer of structural units consisting of block b1 and structural units consisting of block b2.

[0073] (C Block) The C block is formed by radical polymerization of the polymerizable composition (C) for the C block, and is a polymer of the polymerizable composition (C).

[0074] (Vinyl monomer (c-1)) The polymerizable composition (C) contains a vinyl monomer (c-1) having a (meth)acryloyl group and an ethylenically unsaturated group other than the (meth)acryloyl group in one molecule. When the vinyl monomer (c-1) is subjected to living radical polymerization, the (meth)acryloyl group polymerizes preferentially, and most of the ethylenically unsaturated groups other than the (meth)acryloyl group remain unpolymerized. As a result, ethylenically unsaturated groups other than the (meth)acryloyl group are introduced into the formed C block, and the resulting block copolymer is curable. The vinyl monomer (c-1) may be used alone or in combination of two or more types.

[0075] The vinyl monomer (c-1) has one (meth)acryloyl group and at least one ethylenically unsaturated group other than the (meth)acryloyl group in its molecule. Preferably, the vinyl monomer (c-1) has one (meth)acryloyl group and one ethylenically unsaturated group other than the (meth)acryloyl group in its molecule. The ethylenically unsaturated group other than the (meth)acryloyl group means a group containing a radically polymerizable carbon-carbon double bond other than the (meth)acryloyl group, and examples include vinyl group, allyl group, 3-butenyl group, 3-isoprenyl group, cyclohexenyl group, cyclopentenyl group, cyclobutenyl group, dicyclopentenyl group, etc.

[0076] The vinyl monomer (c-1) is preferably a vinyl monomer represented by formula (5).

[0077] [In equation (5), R 51 R represents a hydrogen atom or a methyl group. 52 R represents a single bond or a saturated hydrocarbon group having 1 to 10 carbon atoms. 53 [This represents a hydrogen atom or a methyl group.]

[0078] R 52 Examples of saturated hydrocarbon groups having 1 to 10 carbon atoms represented by include alkylene groups having 1 to 10 carbon atoms. The alkylene group may be linear or branched, but linear is preferred. 52Specific examples of alkylene groups represented by include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, and 1-methylethylene group. 52 The alkylene group represented by preferably has 1 to 5 carbon atoms.

[0079] Examples of vinyl monomers represented by formula (5) include vinyl (meth)acrylate, allyl (meth)acrylate, 3-butenyl (meth)acrylate, 2-methyl-2-propenyl (meth)acrylate, and 3-isoprenyl (meth)acrylate.

[0080] The content of vinyl monomer (c-1) in 100 mol% of the monomer contained in the polymerizable composition (C) is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 97 mol% or more. If the content of vinyl monomer (c-1) is 80 mol% or more, the curability of the colored composition is enhanced.

[0081] A structural unit (X) derived from the vinyl monomer (c-1) and having an ethylenically unsaturated group other than a (meth)acryloyl group is a structural unit in which the (meth)acryloyl group of the vinyl monomer (c-1) polymerizes to form a carbon-carbon single bond, and the ethylenically unsaturated group other than the (meth)acryloyl group remains without polymerization. For example, if the vinyl monomer (c-1) is a vinyl monomer represented by formula (5), then the structural unit (X) is a structural unit represented by formula (5-1).

[0082] [In formula (5-1), R 51 R represents a hydrogen atom or a methyl group. 52 R represents a single bond or a saturated hydrocarbon group having 1 to 10 carbon atoms. 53 [This represents a hydrogen atom or a methyl group.]

[0083] R in equation (5-1) 51 , R 52 and R 53 R in equation (5) 51, R 52 and R 53 It is synonymous with [the above].

[0084] The vinyl monomer (c-1) has a molar volume ratio (X / Y) of structural units (X) derived from vinyl monomer (c-1) that have ethylenically unsaturated groups other than (meth)acryloyl groups, to structural units (Y) derived from vinyl monomer (b-1), which is 0.1 or more, preferably 0.2 or more, more preferably 0.4 or more, and 1.1 or less, preferably 1.0 or less, more preferably 0.9 or less. If the molar volume ratio (X / Y) is 0.1 or more, the curability of the colored composition is increased, and if it is 1.1 or less, the adsorption to the coloring agent is increased. If block B contains multiple types of vinyl monomer (b-1), the molar volume ratio (X / Y) of structural units (X) to structural units (Y) is calculated by determining the molar volume ratio with respect to the structural unit (Y) with the highest content. The molar volume of a structural unit is the molar volume V of each atomic group i constituting the structural unit. i This is the total.

[0085]

[0086] The molar volume of the aforementioned structural unit (X) is 50 cm³. 3 Preferably, 60 cm / mol or more, and more preferably 60 cm / mol or more. 3 / mol or more, more preferably 70cm 3 / mol or more, 150cm 3 Preferably less than / mol, and more preferably 140 cm 3 / mol or less, more preferably 130 cm 3 It is less than or equal to / mol. The molar volume of the structural unit (X) is 50 cm³. 3 If the amount is greater than / mol, aggregation of colorants can be suppressed, and at 150cm 3 Adsorption to the coloring agent increases if the concentration is less than / mol.

[0087] The polymerizable composition (C) may contain other monomers other than the vinyl monomer (c-1) to an extent that does not impair the effects of the present invention. Specific examples of monomers that the polymerizable composition (C) may contain are the same as those exemplified as specific examples of monomers contained in polymerizable composition (A) and polymerizable composition (B).

[0088] Preferably, the polymerizable composition (C) is substantially free of (meth)acrylate (a-1) and / or (meth)acrylate (a-2). The total content of (meth)acrylate (a-1) and (meth)acrylate (a-2) in 100 mol% of monomer in the polymerizable composition (C) is preferably 5 mol% or less, more preferably 3 mol% or less, even more preferably 2 mol% or less, and particularly preferably 1 mol% or less.

[0089] The polymerizable composition (C) preferably contains substantially no nitrogen-containing vinyl monomer (b-1). The content of vinyl monomer (b-1) in 100 mol% of monomer in the polymerizable composition (C) is preferably 5 mol% or less, more preferably 3 mol% or less, even more preferably 2 mol% or less, and particularly preferably 1 mol% or less.

[0090] The various structural units contained in the C block may be contained in the C block in any manner, such as random copolymerization or block copolymerization, and it is preferable that they be contained in a manner of random copolymerization from the viewpoint of uniformity. For example, the C block may be formed by a copolymer of structural units consisting of block c1 and structural units consisting of block c2.

[0091] (Block Copolymer) The structure of the block copolymer is an ABC-type triblock copolymer. By forming an ABC-type triblock copolymer, the structural units of block A and block B are localized, allowing them to efficiently and suitably interact with the colorant, dispersion medium, and binder resin. Furthermore, the localization of the structural units of block C is thought to improve the dispersibility of the colorant and the dispersion performance of the colored composition. The structure of the block copolymer preferably has the arrangement of each block in the order of block A - block B - block C.

[0092] The double bond equivalent of the block copolymer is preferably 300 or more, more preferably 400 or more, even more preferably 500 or more, preferably 6,000 or less, more preferably 3,000 or less, even more preferably 2,000 or less, and particularly preferably 1,200 or less. If the double bond equivalent is 300 or more, the alkali developability of the colored composition is good, and if it is 6,000 or less, the number of double bonds in the copolymer increases, which improves the curability of the colored composition. The method for measuring the double bond equivalent of the block copolymer will be described later.

[0093] The amine value of the block copolymer is preferably 10 mg KOH / g or more, more preferably 25 mg KOH / g or more, even more preferably 55 mg KOH / g or more, preferably 170 mg KOH / g or less, more preferably 120 mg KOH / g or less, and even more preferably 100 mg KOH / g or less, from the viewpoint of adsorption to the coloring agent.

[0094] If the block copolymer contains structural units having acidic groups, the acid value of the block copolymer is preferably 5 mg KOH / g or more, and preferably 50 mg KOH / g or less. By keeping the acid value within this range, the block copolymer can act suitably with alkali-soluble resins without impairing its adsorption properties to colorants. It is also preferable that the block copolymer does not contain structural units having acidic groups.

[0095] The weight-average molecular weight (Mw) of the block copolymer is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, preferably 40,000 or less, more preferably 30,000 or less, and even more preferably 20,000 or less. If the weight-average molecular weight is within the above range, the dispersion performance when used as a dispersant will be better. The molecular weight of the block copolymer is measured by gel permeation chromatography (hereinafter referred to as "GPC").

[0096] The molecular weight distribution (Mw / Mn) of the block copolymer is preferably 3.0 or less, more preferably 2.5 or less, even more preferably 2.0 or less, and particularly preferably 1.5 or less. A molecular weight distribution of 3.0 or less results in better dispersion performance when used as a dispersant. The molecular weight distribution is determined by (weight-average molecular weight of the block copolymer (Mw)) / (number-average molecular weight of the block copolymer (Mn)). A smaller molecular weight distribution value indicates a narrower molecular weight distribution and a copolymer with more uniform molecular weights, with the narrowest molecular weight distribution occurring when the value is 1.0. In other words, the lower limit of the molecular weight distribution is 1.0.

[0097] In the block copolymer, the molar ratio (A block / B block) of the total molar amount of structural units constituting block A to the total molar amount of structural units constituting block B is preferably 0.10 or more, more preferably 0.25 or more, even more preferably 0.60 or more, preferably 9.00 or less, more preferably 4.00 or less, and even more preferably 2.50 or less. If the molar ratio (A block / B block) is 0.10 or more, the dispersibility of the coloring composition is better, and if it is 9.00 or less, the adsorption to the coloring agent is better.

[0098] In the block copolymer, the molar ratio (C block / B block) of the total molar amount of structural units constituting the C block to the total molar amount of structural units constituting the B block is preferably 0.10 or more, more preferably 0.25 or more, even more preferably 0.60 or more, preferably 9.00 or less, more preferably 4.00 or less, and even more preferably 2.50 or less. If the molar ratio (C block / B block) is 0.10 or more, the dispersibility of the colored composition is better, and if it is 9.00 or less, the adsorption to the coloring agent is better.

[0099] (Method for producing block copolymers) Examples of methods for producing the block copolymer include a method in which block A is first produced by a polymerization reaction of vinyl monomers, the monomer of block B is polymerized onto block A, and the monomer of block C is polymerized onto block B; and a method in which block C is first produced, the monomer of block B is polymerized onto block C, and the monomer of block A is polymerized onto block B.

[0100] Radical polymerization is used as the polymerization method for producing the aforementioned block copolymer, and it is preferable to use living radical polymerization. In other words, it is preferable that the block copolymer is polymerized by living radical polymerization.

[0101] Living radical polymerization is a process in which, among the four elementary reactions in chain polymerization—initiation, growth, termination, and chain transfer—side reactions such as termination and chain transfer are substantially absent, and the reaction sites (polymerization growth ends) remain uninactivated, allowing vinyl monomers to react and polymer chains to grow. Therefore, it is easy to produce copolymers with a narrow molecular weight distribution and a uniform composition. Furthermore, living radical polymerization maintains the simplicity and versatility of conventional radical polymerization while allowing for precise control of molecular weight distribution and easy production of copolymers with a uniform composition.

[0102] A preferred method for producing the block copolymer comprises: a first step of radical polymerization of the polymerizable composition (A) to form an A block; a second step of radical polymerization of the polymerizable composition (B) onto the A block to obtain an AB diblock copolymer; and a third step of radical polymerization of the polymerizable composition (C) onto the AB diblock copolymer to obtain an ABC triblock copolymer. It is presumed that by using such a production method, when polymerizing the polymerizable composition (C) onto the AB block, the (meth)acryloyl group of the vinyl monomer (c-1) can be preferentially radical-polymerized, and the high reactivity of other monomer radicals can suppress their reaction to the ethylenically unsaturated group of the structural unit (X) and thus prevent radical polymerization.

[0103] Living radical polymerization includes methods that utilize compounds capable of generating nitroxide radicals, depending on the method used to stabilize the polymerization growth ends (nitroxide method; NMP method); methods that use metal complexes such as copper and ruthenium, with halogenated compounds as polymerization initiators, and polymerize from those initiators in a living manner (ATRP method); methods that use dithiocarboxylic acid esters or xantate compounds (RAFT method); methods that use organotellurium compounds (TERP method); methods that use organiodine compounds (ITP method); and methods that use iodine compounds as polymerization initiators and organic compounds such as phosphorus compounds, nitrogen compounds, oxygen compounds, or hydrocarbons as catalysts (reversible transfer catalytic polymerization; RTCP method, reversible catalyst-mediated polymerization; RCMP method).

[0104] Among these methods, the TERP method is preferred from the viewpoint of the diversity of monomers that can be used, molecular weight control in the polymer range, and uniform composition or coloration. The TERP method is a method for polymerizing radical polymerizable compounds (vinyl monomers) using an organotellurium compound as a chain transfer agent, and is described, for example, in International Publication Nos. 2004 / 14848, 2004 / 14962, 2004 / 072126, 2004 / 096870, and 2020 / 116144.

[0105] Specific polymerization methods of the TERP method include the following (a) to (d): (a) A method of polymerizing vinyl monomer using an organic tellurium compound represented by formula (T1). (b) A method of polymerizing vinyl monomer using a mixture of an organic tellurium compound represented by formula (T1) and an azo polymerization initiator. (c) A method of polymerizing vinyl monomer using a mixture of an organic tellurium compound represented by formula (T1) and an organic diterlide compound represented by formula (T2). (d) A method of polymerizing vinyl monomer using a mixture of an organic tellurium compound represented by formula (T1), an azo polymerization initiator, and an organic diterlide compound represented by formula (T2).

[0106] R t1 -Te-CR t2 R t3 R t4 (T1) R t1 -Te-Te-R t1 (T2) [In equations (T1) and (T2), R t1 R represents an alkyl group, aryl group, or aromatic heterocyclic group having 1 to 8 carbon atoms. t2 and R t3 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. t4 This 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.

[0107] The organic tellurium compounds represented by formula (T1) include, specifically, ethyl = 2-methyl-2-n-butylteranyl propionate, ethyl = 2-n-butylteranyl propionate, (2-hydroxyethyl) = 2-methyl-methylteranyl propionate, and other organic tellurium compounds described in International Publication Nos. 2004 / 14848, 2004 / 14962, 2004 / 072126, 2004 / 096870, and 2020 / 116144.

[0108] Specific examples of the organic diterlide compound represented by formula (T2) include dimethyl diterlide and dibutyl diterlide. The azo polymerization initiator can be any azo polymerization initiator used in normal radical polymerization without particular restrictions, such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(1-cyclohexanecarbonitride), dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis(N-butyl-2-methylpropionamide).

[0109] The polymerization step involves mixing a vinyl monomer, an organic tellurium compound of formula (T1), and, depending on the type of vinyl monomer, an azo polymerization initiator and / or an organic diterlide compound of formula (T2) in a container purged with an inert gas. Examples of inert gases used include nitrogen, argon, and helium. Argon and nitrogen are preferred. The amount of vinyl monomer used in (a), (b), (c), and (d) above may be adjusted as appropriate depending on the desired properties of the copolymer.

[0110] The polymerization reaction can be carried out without a solvent, or it may be carried out by using an aprotic solvent or a protic solvent commonly used in radical polymerization and stirring the mixture. Examples of aprotic solvents that can be used include acetonitrile, methyl ethyl ketone, anisole, benzene, toluene, propylene glycol monomethyl ether acetate, ethyl acetate, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetone, dioxane, chloroform, carbon tetrachloride, etc. Examples of protic solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, diacetone alcohol, etc. The solvent may be used alone or in combination of two or more. The amount of the solvent used may be adjusted as appropriate. For example, 0.01 ml to 50 ml is preferable per 1 g of the vinyl monomer. In the polymerization reaction, in addition to the solvent, a surfactant and / or a dispersant can also be used. The reaction temperature and reaction time may be adjusted as appropriate according to the molecular weight or molecular weight distribution of the obtained copolymer, but usually, it is stirred at 0°C to 150°C for 1 minute to 100 hours. At this time, the pressure is usually carried out at normal pressure, but it may be pressurized or depressurized. Also, the polymerization reaction may be carried out by light irradiation. After the completion of the polymerization reaction, the target copolymer can be separated from the obtained reaction mixture by ordinary separation and purification means such as removing the used solvent and residual vinyl monomer.

[0111] The growing end of the copolymer obtained by the polymerization reaction is -TeR derived from a tellurium compound t1 (wherein, R t1The form is the same as described above, and although it is deactivated by handling in air after the polymerization reaction is complete, tellurium atoms may remain. Copolymers with tellurium atoms remaining at the ends may be discolored or have poor thermal stability, so it is preferable to remove the tellurium atoms. Methods for removing tellurium atoms include radical reduction methods; adsorption methods using activated carbon, etc.; and adsorption methods using ion exchange resins, etc. These methods can also be used in combination. The other end of the copolymer obtained by the polymerization reaction (the end opposite to the growth end) is -CR derived from the tellurium compound. t2 R t3 R t4 (In the formula, R t2 , R t3 and R t4 The form is the same as described above. Therefore, the copolymer obtained by the TERP method does not have substituents containing sulfur atoms at its terminals.

[0112] <Dispersant> The dispersant of the present invention contains the block copolymer as a main component (50% by mass or more). The content of the block copolymer in the dispersant is preferably 70% by mass or more, more preferably 90% by mass or more. The dispersant may consist only of the block copolymer.

[0113] The dispersant of the present invention facilitates the dispersion of colorants when prepared as a dispersant solution before the preparation of the colored composition. The solvent used in the dispersant solution is preferably one that can dissolve the dispersant, does not react with these components, and is moderately volatile. Examples of such solvents include the dispersion media used in the colored composition described later. The solvent content in the dispersant solution is not particularly limited and can be adjusted as appropriate. The upper limit of the solvent content in the dispersant solution is usually 99% by mass. The lower limit of the dispersion media content in the dispersant solution is usually 10% by mass, preferably 30% by mass, considering the viscosity suitable for the production of the colored composition described later.

[0114] The block copolymer exhibits an effect of enhancing the dispersibility of colorants because block A has appropriate compatibility with the dispersion medium and block B has high adsorption to colorants. In other words, the dispersant of the present invention is a component that disperses colorants well by this effect, and is therefore not particularly limited to the type of colorant to be dispersed. Furthermore, the block copolymer has a moderate molar volume of block C, which has ethylenically unsaturated groups, and does not easily inhibit the adsorption of block B to colorants, so it not only has excellent dispersibility of colorants and dispersion performance of colored compositions, but also possesses UV curability. Because the dispersant of the present invention has not only excellent dispersibility of colorants but also UV curability, it can be suitably used as a dispersant for colored compositions for color filters. In addition, because the dispersant of the present invention has high dispersibility of colorants, it can also be used in inkjet inks, printing inks, writing instrument inks, paints, etc. By appropriately changing the composition of the block copolymer, it can be used not only in colored compositions using organic solvents but also in colored compositions using aqueous solvents.

[0115] <Coloring Composition> The coloring composition of the present invention contains the dispersant, coloring agent and dispersion medium. The coloring composition of the present invention is suitable for use as a coloring composition for color filters because it has not only dispersion performance of the coloring agent but also UV curability.

[0116] (Coloring agent) The type of coloring agent can be appropriately selected according to its application and is not particularly limited. The colored composition preferably contains a pigment as a coloring agent. The pigment may be either an organic pigment or an inorganic pigment, but an organic pigment mainly composed of an organic compound is particularly preferred. Examples of pigments include red pigments, yellow pigments, orange pigments, blue pigments, green pigments, purple pigments, and other pigments of various colors. Examples of pigment structures include azo pigments such as monoazo pigments, diazo pigments, and condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments, and other polycyclic pigments. The colored composition may contain only one type of pigment or multiple types.

[0117] Specific examples of pigments include red pigments such as 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, 168, 177, 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264, 291, etc.; C. I. Pigment Yellow: Yellow pigments such as 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, etc.; C.I. Pigment Orange: Orange pigments such as 36, 38, 43, etc.; C.I. Pigment Blue: Blue pigments such as 15, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, etc.; C.I. Examples of green pigments include C.I. Pigment Green 7, 36, 58, 59, 62, 63, aluminum phthalocyanine, polyhalogenated aluminum phthalocyanine, aluminum phthalocyanine hydroxide, diphenoxyphosphinyloxyaluminum phthalocyanine, diphenylphosphinyloxyaluminum phthalocyanine, polyhalogenated diphenoxyphosphinyloxyaluminum phthalocyanine, and polyhalogenated diphenylphosphinyloxyaluminum phthalocyanine; purple pigments such as C.I. Pigment Violet 23, 32, 50, and preferably C.I. Pigment Red 177, 254, 255, 264, 291; C.I. Pigment Blue 15, 15:2, 15:3, 15:4, 15:6, 16; C.I. Pigment Green values ​​are 7, 36, 58, 59, 62, and 63.

[0118] When forming a light-shielding material such as a black matrix for a color filter using the colored composition of the present invention, a black pigment can be used as the coloring agent. The black pigment may be used alone, or it may be used in combination with the aforementioned red, green, blue, and other pigments. Examples of black pigments that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferred from the viewpoint of light-shielding rate and image characteristics.

[0119] Furthermore, the coloring agent may contain a dye derivative as a dispersion aid. If the block copolymer has a basic group, it is preferable to include an acidic dye derivative having an acidic group as the dye derivative in order to adsorb it by ionic bonding with the basic group in the block copolymer contained in the dispersant. This dye derivative has an acidic group introduced into its dye skeleton. The dye skeleton is preferably the same or similar skeleton as the coloring agent constituting the coloring composition, or the same or similar skeleton as the compound that is the raw material for the coloring agent. Specific examples of dye skeletons include azo dye skeletons, phthalocyanine dye skeletons, anthraquinone dye skeletons, triazine dye skeletons, acridine dye skeletons, perylene dye skeletons, etc. The acidic group introduced into the dye skeleton is preferably a carboxyl group, a phosphate group, or a sulfonic acid group. Sulfonic acid groups are preferred for ease of synthesis and due to their acidity. The acidic group may be directly bonded to the dye skeleton, or it may be bonded to the dye skeleton via hydrocarbon groups such as alkyl groups or aryl groups; or via ester, ether, sulfonamide, or urethane bonds. There are no particular limitations on the amount of dye derivative used, but it is preferably 4 to 17 parts by mass per 100 parts by mass of coloring agent.

[0120] The particle size of the coloring agent can be appropriately selected according to its application and is not particularly limited. Preferably, from the viewpoint of high transparency and high contrast of the colored composition, the particle size of the coloring agent is 10 nm to 150 nm.

[0121] From the viewpoint of brightness, the content of the coloring agent in the colored composition is preferably 10% to 100% by mass, more preferably 20% to 80% by mass, and even more preferably 30% to 60% by mass, relative to the total solid content of the colored composition. Here, the solid content refers to components other than the dispersion medium described later.

[0122] The amount of dispersant in the colored composition relative to the coloring agent is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 10 to 80 parts by mass, per 100 parts by mass of the coloring agent. The viscosity of the colored composition is good when the amount of dispersant is within the above range.

[0123] (Dispersion medium) Any dispersion medium can be used in the present invention as appropriate, as long as it disperses or dissolves the other components constituting the colored composition, does not react with these components, and is moderately volatile. For example, conventionally known organic solvents can be used, such as glycol monoalkyl ethers, glycol dialkyl ethers, glycol alkyl ether acetates, alkyl acetates, ethers, ketones, monohydric or polyhydric alcohols, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, linear or cyclic esters, halogenated hydrocarbons, ether ketones, nitriles, etc., and these can be used individually or in combination of two or more. From the viewpoint of dispersibility of colorants, solubility of dispersants, and coatability of colored compositions, one or more organic solvents selected from the group consisting of glycol alkyl ether acetates, glycol monoalkyl ethers, monohydric or polyhydric alcohols, and linear or cyclic esters can be used in combination.

[0124] Examples of the glycol alkyl ether acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate. Examples of the glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether. Examples of the monohydric or polyhydric alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, methoxymethyl pentanol, glycerin, and benzyl alcohol.Examples of the aforementioned chain-like or cyclic esters include amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone.

[0125] Among organic solvents, glycol alkyl ether acetates are preferred because they offer a good balance of applicability and surface tension, and the solubility of the components in the colored composition is relatively high. Glycol alkyl ether acetates may be used alone or in combination with other organic solvents. It is also preferable to use organic solvents with a boiling point of 150°C or higher. By using organic solvents with a high boiling point, it is possible to suppress the destruction of the interrelationships of the colored composition due to rapid drying of the colored composition.

[0126] The boiling point of the organic solvent at atmospheric pressure (1013.25 hPa) is preferably 100°C to 220°C. If the coloring composition contains a large amount of organic solvent with a boiling point above 220°C, when the coating film applied to the coloring composition is pre-baked during the production of the color filter described later, the organic solvent may not evaporate sufficiently and may remain in the dried coating film, potentially reducing the heat resistance of the dried coating film. Furthermore, if the composition contains a large amount of organic solvent with a boiling point below 100°C, it becomes difficult to apply the coating uniformly without unevenness, potentially resulting in a coating film with excellent surface smoothness.

[0127] The content of the dispersion medium in the colored composition is not particularly limited and can be adjusted as appropriate. The upper limit of the dispersion medium content in the colored composition is usually 99% by mass. The lower limit of the dispersion medium content in the colored composition is usually 70% by mass, taking into consideration the viscosity suitable for coating the colored composition. The dispersion medium can be used as a solvent for dissolving and removing precipitates formed from the colored composition.

[0128] (Binder Resin) The colored composition of the present invention may contain a binder resin (except for the block copolymer of the present invention). Examples of binder resins include alkali-soluble resins, polymerizable compounds, thermosetting resins, thermoplastic resins, etc. These can be used individually or in combination of two or more. Among these, alkali-soluble resins and / or polymerizable compounds are preferred.

[0129] The binder resin content in the colored composition is preferably 1% to 70% by mass, and more preferably 5% to 50% by mass, based on the total amount of binder resin used and the total solid content of the colored composition.

[0130] (Alkali-soluble resin) The alkali-soluble resin is not particularly limited as long as it acts as a binder for the coloring agent and is soluble in the developing solution, preferably an alkaline developing solution, used in the developing process when manufacturing the color filter, but it is preferable that it is a polymer having acidic groups such as carboxyl groups and phenolic hydroxyl groups.

[0131] Examples of alkali-soluble resins include polymers having carboxyl groups; polymers obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups of a copolymer of a vinyl monomer having epoxy groups and another vinyl monomer, or polymers obtained by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups produced by the addition reaction. These can be used individually or in combination of two or more.

[0132] Polymers having carboxyl groups as alkali-soluble resins are not particularly limited as long as they have carboxyl groups, and are usually obtained by polymerizing vinyl monomers having carboxyl groups. Examples of vinyl monomers having carboxyl groups include (meth)acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2-((meth)acryloyloxy)ethyl hydrogen succinate, 2-((meth)acryloyloxy)ethyl hydrogen hexahydrophthalate, 2-((meth)acryloyloxy)ethyl hydrogen phthalate, 2-carboxyethyl (meth)acrylic acid, and caprolactone adducts of (meth)acrylic acid, with (meth)acrylic acid being preferred.

[0133] Polymers having carboxyl groups as alkali-soluble resins include vinyl monomers having carboxyl groups, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 3-hydroxy (meth)acrylate. Roxypropyl, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycerol mono(meth)acrylate, glycidyl (meth)acrylate, methyl (3,4-epoxycyclohexyl)(meth)acrylate, styrene, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, and other vinyl monomers without carboxyl groups may be copolymerized, and preferably a copolymer of a vinyl monomer having a carboxyl group and another vinyl monomer without a carboxyl group. The polymerization method of these copolymers is not particularly limited, but living radical polymerization is preferred from the viewpoint of alkali solubility. Furthermore, these copolymers may be formed in any form, such as random copolymerization or block copolymerization, but random copolymerization is preferred.

[0134] Specific examples of polymers having carboxyl groups as alkali-soluble resins include copolymers of (meth)acrylic acid and butyl (meth)acrylate, copolymers of (meth)acrylic acid and benzyl (meth)acrylate, copolymers of (meth)acrylic acid, butyl (meth)acrylate and benzyl (meth)acrylate, copolymers of (meth)acrylic acid, styrene and α-methylstyrene, and copolymers of (meth)acrylic acid and cyclohexylmaleimide.

[0135] The polymer having a carboxyl group as an alkali-soluble resin preferably has a structural content derived from vinyl monomers having a carboxyl group of 5% to 90% by mass, more preferably 20% to 70% by mass. Furthermore, the structural unit content derived from (meth)acrylate in the polymer is preferably 70% by mass or more.

[0136] The alkali-soluble resin may have a radically polymerizable carbon-carbon double bond in its side chain. Having a double bond in the side chain enhances the photocurability of the colored composition according to the present invention, thereby further improving resolution and adhesion. As a method for introducing a radically polymerizable carbon-carbon double bond in the side chain, for example, a compound such as glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, or o-(or m-, or p-) vinylbenzylglycidyl ether is reacted with the acidic group of the alkali-soluble resin.

[0137] If the Mw of the alkali-soluble resin is 3,000 or higher, the heat resistance and film strength of the colored layer formed from the colored composition will be good, and if it is 100,000 or lower, the alkali developability when the colored composition is used as the colored layer will be even better.

[0138] The acid value of the alkali-soluble resin is preferably 20 mg KOH / g to 170 mg KOH / g, more preferably 90 mg KOH / g to 150 mg KOH / g. When the acid value is 20 mg KOH / g or higher, the alkali developability when the colored composition is used as a colored layer is further improved, and when it is 170 mg KOH / g or lower, the heat resistance is improved.

[0139] In the colored composition, the content of alkali-soluble resin is preferably 5 to 200 parts by mass, more preferably 20 to 80 parts by mass, per 100 parts by mass of coloring material.

[0140] (Polymerizable Compounds) Examples of polymerizable compounds include polymerizable resins such as those obtained by introducing crosslinking groups such as (meth)acrylic compounds and cinnamic acid via isocyanate groups, aldehyde groups, epoxy groups, etc., to linear polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups; compounds having one polymerizable unsaturated bond in the molecule, such as monofunctional (meth)acrylic monomers (alkyl (meth)acrylate, aralkyl (meth)acrylate, etc.); and compounds having two or more polymerizable unsaturated bonds in the molecule, such as polyfunctional (meth)acrylic monomers (di(meth)acrylate of dihydric alcohols, poly(meth)acrylate of trihydric or higher polyhydric alcohols, etc.). Examples of polymerizable unsaturated bonds include carbon-carbon double bonds and carbon-carbon triple bonds. These can be used individually or in combination of two or more. Among these, compounds having two or more polymerizable unsaturated bonds in the molecule are preferred.

[0141] Examples of monomers having two or more polymerizable unsaturated bonds in their molecule as polymerizable compounds include bisphenol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, opentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tris(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0142] The polymerizable compound content in the coloring composition is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, per 100 parts by mass of the coloring agent. If the polymerizable compound content is within the above range, sufficient curability and good alkali developability are obtained. An alkali-soluble resin and a polymerizable compound may be used in combination as the binder resin.

[0143] (Thermosetting resins, thermoplastic resins) Examples of thermosetting resins and thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resins, phenolic resins, polyester resins, (meth)acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclocompound rubber, epoxy resins, celluloses, polybutadiene, polyimide resins, benzoguanamine resins, melamine resins, urea resins, etc.

[0144] (Photopolymerization initiator) The colored composition of the present invention may optionally contain a photopolymerization initiator. This can impart radiation sensitivity to the colored composition. The photopolymerization initiator is a compound that generates an active species capable of initiating polymerization of the block copolymer and polymerizable compound of the present invention upon exposure to radiation such as visible light, ultraviolet light, far-infrared rays, electron beams, and X-rays.

[0145] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred, and more preferably molecular cleavage-type photoradical polymerization initiators and hydrogen abstraction-type photoradical polymerization initiators. Examples of the molecular cleavage-type photoradical polymerization initiators include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. Examples of the hydrogen abstraction type photoradical polymerization initiator include benzophenone, 4-phenylbenzophenone, isophthalphenone, and 4-benzoyl-4'-methyl-diphenyl sulfide. The photopolymerization initiator can be used alone or in combination of two or more types. In addition, a molecular cleavage type photoradical polymerization initiator and a hydrogen abstraction type photoradical polymerization initiator may be used in combination.

[0146] The amount of photopolymerization initiator in the colored composition is preferably 0.01 to 120 parts by mass, more preferably 0.1 to 100 parts by mass, and even more preferably 1 to 40 parts by mass, based on 100 parts by mass of the total of the block copolymer and polymerizable compound of the present invention. In this case, if the amount of photopolymerization initiator is too low, curing may be insufficient upon exposure, while if it is too high, the formed colored layer tends to detach easily from the substrate during development.

[0147] (Other Compounding Agents) In addition to the compounding agents mentioned above, other compounding agents may be added to the colored composition of the present invention, provided that they do not impair the desirable physical properties of the present invention. Examples of other compounding agents include dispersants other than the block copolymer of the present invention (urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, aliphatic-modified polyester-based dispersants, etc.), sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, plasticizers, organic carboxylic acid compounds, organic carboxylic acid anhydrides, antioxidants, ultraviolet absorbers, light stabilizers, pH adjusters, preservatives, fungicides, anti-aggregation agents, adhesion improvers, developer improvers, and storage stabilizers.

[0148] Examples of sensitizing dyes include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone, 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, and 2,5-bis(p-diethylaminophenyl)1,3,4- Examples include oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc.

[0149] Examples of thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, and β-naphthol.

[0150] Nonionic surfactants include 1,1,2,2-tetrafluorooctyl(1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, and 1,1,2,2,3,3-hexafluoro Examples of polyoxyethylene surfactants include fluorinated surfactants such as can; silicone surfactants; polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, and polyoxyethylene sorbitol fatty acid esters. Examples of anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, higher alcohol sulfate esters, aliphatic alcohol sulfate esters, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, and special polymer surfactants. Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.Examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, and amino acids.

[0151] Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetylglycerin.

[0152] Examples of organic carboxylic acid compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid; aliphatic tricarboxylic acids such as tricarbaryl acid and aconitic acid; aromatic carboxylic acids in which a carboxyl group is directly bonded to a phenyl group, such as benzoic acid, phthalic acid, trimesic acid, pyropetic acid, and merophanic acid; and aromatic carboxylic acids in which a carboxyl group is bonded to a phenyl group via a carbon bond, such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, phenylsuccinic acid, and cinnamilindenic acid. The inclusion of organic carboxylic acid compounds can improve alkali developability and soil staining. Examples of organic carboxylic acid anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic anhydride, n-octadecylsuccinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. The inclusion of organic carboxylic acid anhydrides can improve alkali developability and reduce soil staining.

[0153] <Method for Producing Colored Compositions> Colored compositions can be prepared by mixing a colorant, a dispersant (or dispersant solution), a dispersion medium, and, if necessary, a binder resin, a photopolymerization initiator, and other compounding agents. Mixing can be done using, for example, a paint shaker, bead mill, ball mill, dissolver, or kneader. It is preferable to filter the colored composition after mixing. If the colored composition is alkaline developable, it can be suitably used for color filters. As the alkaline developer, an aqueous solution containing an organic solvent or surfactant and an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide can be used.

[0154] <Color Filter> The color filter of the present invention comprises a colored layer formed using the coloring composition described above.

[0155] One example of a method for manufacturing a color filter is as follows: First, a coloring composition in which a red pigment is dispersed is applied to a transparent substrate such as a thermoplastic resin sheet (e.g., polyester resin, polyolefin resin, polycarbonate resin, polymethyl methacrylate resin), a thermosetting resin sheet (e.g., epoxy resin, unsaturated polyester resin, poly(meth)acrylic resin), or various types of glass. Then, pre-baking is performed to evaporate the solvent (dispersion medium) and form a coating film. Next, this coating film is exposed to light through a photomask, and then developed using an alkaline developer (an aqueous solution containing an organic solvent or surfactant and an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide) to dissolve and remove the unexposed parts of the coating film. Subsequently, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined sequence. Next, using a green coloring composition or a blue coloring composition, the same procedure as above is followed to apply, pre-bake, expose, develop, and post-bake each coloring composition to sequentially form a green pixel array and a blue pixel array on the same substrate. This results in a color filter in which pixel arrays of the three primary colors, red, green, and blue, are arranged on a substrate. However, in this invention, the order in which the pixels of each color are formed is not limited to the above. Furthermore, a black matrix may be provided on the transparent substrate used to form the pixel arrays of the three primary colors, red, green, and blue.

[0156] When applying the colored composition to the substrate, an appropriate coating method such as spray coating, roll coating, spin coating, slit die coating, or bar coating can be used, but spin coating or slit die coating is particularly preferred. After forming a protective film on the pixel pattern obtained in this way, a transparent conductive film (such as ITO) is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to create a color filter.

[0157] The color filter of the present invention has high brightness and dimensional accuracy, and can be suitably used in color liquid crystal display elements, color image tube elements, color sensors, organic EL display elements, electronic paper, and the like.

[0158] Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples, and can be appropriately modified and implemented without changing the gist thereof. The polymerization rate, weight average molecular weight, molecular weight distribution, amine value, and double bond equivalent of the block copolymer, as well as the physical properties of the coloring composition, were evaluated according to the following methods.

[0159] The meanings of the abbreviations are as follows. BTEE: ethyl = 2-methyl-2-n-butyltellanyl-propionate DBDT: dibutylditelluride AIBN: 2,2'-azobis(isobutyronitrile) BMA: n-butyl methacrylate CL5MA: 5mol caprolactone adduct of 2-hydroxyethyl methacrylate M4EGM: polyethylene glycol (degree of polymerization = 4) methyl ether methacrylate BzMA: benzyl methacrylate MAA: methacrylic acid DMAEMA: dimethylaminoethyl methacrylate VMA: vinyl methacrylate PMA: propylene glycol monomethyl ether acetate

[0160] [Evaluation method] (Polymerization rate) Using a nuclear magnetic resonance (NMR) measurement device (manufactured by Bruker BioSpin, model: AVANCE500 (frequency 500 MHz)), 1 1H-NMR was measured (solvent: CDCl3, internal standard: tetramethylsilane). For the obtained NMR spectrum, the integration ratio of the peaks derived from the monomer and the peaks derived from the polymer was determined, and the polymerization rate of the monomer was calculated.

[0161] (Weight-average molecular weight and molecular weight distribution) These were determined by gel permeation chromatography (GPC) using a high-performance liquid chromatograph (Tosoh, model HLC-8320). One SHODEX KF-603 column (Φ6.0 mm × 150 mm) (SHODEX) was used, lithium bromide (30 mmol / L)-acetic acid (30 mmol / L)-N-methylpyrrolidone was used as the mobile phase, and a differential refractive index detector was used. The measurement conditions were a column temperature of 40°C, a sample concentration of 20 mg / mL, a sample injection volume of 10 μL, and a flow rate of 0.2 mL / min. Calibration curves were created using polystyrene (molecular weights 70,500, 37,900, 19,920, 10,200, 4,910, 2,630, 1,150) as standard substances, and the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured. The molecular weight distribution (Mw / Mn) was calculated from these measurements.

[0162] (Double bond equivalent) The double bond equivalent of the block copolymer was calculated using the following formula: Double bond equivalent = Number average molecular weight of copolymer / Number of double bonds per copolymer molecule Here, the number of double bonds per block copolymer molecule was measured using an NMR analyzer (Bruker BioSpin, model: AVANCE500 (frequency 500MHz)) for a block copolymer (sample: 100 mg) 1 The substance was determined from the resulting NMR spectrum obtained by performing 1H-NMR measurements (solvent: CDCl3, internal standard: tetramethylsilane).

[0163] (Amine Value) The amine value represents the mass of the basic component and the equivalent amount of potassium hydroxide per gram of solid content. The sample was dissolved in tetrahydrofuran, and the resulting solution was titrated with hydrochloric acid (0.1 mol / L)-propanol solution using a potentiometric titrator (product name: GT-06, manufactured by Nitto Seikou Analytech). The amine value was calculated using the following formula, with the inflection point of the titration pH curve as the titration endpoint: B = 56.11 × Vs × 0.1 × f / w B: Amine value (mgKOH / g) Vs: Amount of hydrochloric acid (0.1 mol / L)-propanol solution used for titration (mL) f: Titer of hydrochloric acid (0.1 mol / L) (propanol) w: Mass of the sample (g) (converted to solid content)

[0164] (Acid Value) The acid value represents the mass of potassium hydroxide required to neutralize the acidic component per gram of solid content. The sample was dissolved in tetrahydrofuran, and a few drops of 1.0 w / v% phenolphthalein ethanol (90) solution were added to the resulting solution as an indicator. The solution was then titrated with potassium hydroxide (0.1 mol / L)-ethanol solution. The titration endpoint was defined as the point where a slight reddish tint remained, and the acid value was calculated using the following formula: A = 56.11 × Vs × 0.1 × f / w A: Acid value (mgKOH / g) Vs: Amount of potassium hydroxide (0.1 mol / L)-ethanol solution used for titration (mL) f: Titer of potassium hydroxide (0.1 mol / L)-ethanol solution w: Mass of the sample (g) (converted to solid content)

[0165] (Viscosity) Viscosity (mPa·s) was measured using an E-type viscometer (product name: RE-80L, manufactured by Toki Sangyo Co., Ltd.) with a cone rotor (0.8° × R24) at 25°C and a rotor speed of 50 rpm. Measurements were taken for the initial viscosity immediately after preparation of the colored composition and the viscosity after storage of the prepared colored composition at 40°C for one week. The rate of change in viscosity (= (viscosity after storage - initial viscosity) / initial viscosity × 100) was calculated from the initial viscosity and the viscosity after storage.

[0166] (Curable) 2,4,6-trimethylbenzoyldiphenylphosphine oxide was mixed into the colored composition to a concentration of 1% by mass. This colored composition was applied to a glass substrate using a spin coater and then dried under reduced pressure at 80°C for 1 hour. After that, it was cured using a UV lamp irradiation device (Light Hammer 6) at a rate of 300 mJ / cm². 2 A cured film was prepared by irradiating it with ultraviolet light. The prepared cured film was immersed in a potassium hydroxide aqueous solution (concentration: 0.1 mol / L), and the solubility of the cured film was visually assessed. Films that did not dissolve were evaluated as "○", and those that dissolved were evaluated as "×".

[0167] <Synthesis of Block Copolymer> (Block Copolymer No. 1) In a flask equipped with a nitrogen inlet tube and a stirrer, 18.45 g of BMA, 55.21 g of CL5MA, 0.329 g of AIBN, and 73.65 g of PMA were charged. After purging with nitrogen, 3.00 g of BTEE and 1.85 g of DBDT were added, and the mixture was reacted at 60°C for 17.5 hours to polymerize Block A. The polymerization rate was 99%.

[0168] A mixed solution of 23.20 g of DMAEMA and 23.21 g of PMA, which had been pre-purged with nitrogen, was added to the reaction solution, and the reaction was carried out at 60°C for 25 hours to polymerize block B. The polymerization rate was 99%.

[0169] A mixed solution of 26.37 g of pre-purged nitrogen-filled VMA, 0.038 g of AIBN, and 23.80 g of PMA was added to the reaction solution, and the reaction was carried out at 60°C for 24 hours to polymerize the C block. The polymerization rate was 70%.

[0170] After the reaction was complete, the reaction solution was poured into a stirred n-heptane solution. The precipitated polymer was filtered by suction and dried to obtain block copolymer No. 1. The obtained block copolymer No. 1 had an Mw of 16,684, an Mw / Mn of 2.35, an amine value of 78 mgKOH / g, and a double bond equivalent of 609.

[0171] (Block Copolymers No. 2-6) Block copolymers No. 2-6 were prepared in the same manner as block copolymer No. 1. Table 2 shows the monomers, polymerization agents, solvents, reaction conditions, and polymerization rates used. Block copolymers No. 4 and 5 are AB diblock copolymers, and in block copolymer No. 5, the B block was polymerized first, and then polymerizable composition (A) was polymerized onto this B block.

[0172] (Block Copolymer No. 7) A solution was prepared by dissolving 34.6 g of block copolymer No. 6 in 48.4 g of PMA solvent. To this solution, 4.52 g of glycidyl methacrylate, 632 μL of triethylamine, and 8 mg of 2,2,6,6-tetramethylpiperidine-1-oxyl were added, and the mixture was reacted at 80°C for 24 hours. After the reaction was complete, the reaction solution was poured into a stirred n-heptane. Block copolymer No. 7 was obtained by suction filtration and drying of the precipitated polymer. The obtained block copolymer No. 7 had an Mw of 21,527, an Mw / Mn of 1.86, an amine value of 76 mg KOH / g, and a double bond equivalent of 1491.

[0173]

[0174] Table 3 shows the composition of each polymerizable composition, Mw, Mw / Mn, amine value, and double bond equivalent of each copolymer. The molar ratios (Block A / Block B) and (Block C / Block B) were calculated from the charge ratio and polymerization rate of the monomers used in the polymerization reaction.

[0175]

[0176] <Synthesis of Alkali-Soluble Resin (Binder Resin)> 40.0 g of MAA, 160.0 g of BzMA, and 580.0 g of PMA were charged into a flask equipped with an argon gas inlet tube and a stirrer. After purging with argon, 4.0 g of AIBN, 6.0 g of n-dodecanethiol, and 20.0 g of PMA were added and the mixture was heated to 90°C. While maintaining the solution at 90°C, 80.0 g of MAA, 320.0 g of BzMA, 8.0 g of AIBN, 12.0 g of n-dodecanethiol, and 50.0 g of PMA were added dropwise over 1.5 hours. Sixty minutes after the dropwise addition was complete, the temperature was raised to 110°C, and 0.8 g of AIBN and 10.0 g of PMA were added and reacted for 1 hour. Then, another 0.8 g of AIBN and 10.0 g of PMA were added and reacted for 1 hour. Finally, another 0.8 g of AIBN and 10.0 g of PMA were added and reacted for 1 hour.

[0177] The resulting reaction solution was cooled to room temperature, and 240.0 g of PMA was added to obtain an alkali-soluble resin solution with a non-volatile content of 39.5%. The Mw of the alkali-soluble resin was 9,150, the Mw / Mn ratio was 1.92, and the acid value was 128 mg KOH / g.

[0178] (Colored Compositions No. 1-5, 7) Colored compositions were prepared using block copolymers No. 1-5, 7 obtained above. Specifically, 1.8 g of coloring agent (C.I. Pigment Red 254, trade name: Irgafor Red BKCF, manufactured by Ciba Specialty Chemicals) was added to a bead mill (product name: DISPERMAT CA, manufactured by VMA-GETZMANN GmbH), 40 parts by mass of block copolymer per 100 parts by mass of coloring agent (based on solid content), 40 parts by mass of alkali-soluble resin per 100 parts by mass of coloring agent (based on solid content), and PMA so that the coloring agent concentration was 10% by mass. Then 50 g of zirconia beads (φ0.3 mm) were added and the mixture was stirred for 2 hours. After stirring was complete, the beads were filtered off to prepare colored compositions No. 1-5, 7. The obtained colored compositions were evaluated, and the results are shown in Table 4.

[0179]

[0180] Block copolymers No. 1 to 3 are formed by radical polymerization of a polymerizable composition (A) containing a (meth)acrylate (a-1) having a hydroxyl group and / or a (meth)acrylate (a-2) having an alkoxy group for block A, by radical polymerization of a polymerizable composition (B) containing a vinyl monomer (b-1) having a nitrogen-containing functional group for block B, and by radical polymerization of a polymerizable composition (C) containing a vinyl monomer (c-1) having an (meth)acryloyl group and an ethylenically unsaturated group other than a (meth)acryloyl group in one molecule, with a molar volume ratio (X / Y) of the structural unit (X) to the structural unit (Y) of 0.1 to 1.1. Colored compositions No. 1 to 3 using these block copolymers No. 1 to 3 as dispersants exhibited high dispersion performance and excellent curability. In particular, block copolymer No. 1 also exhibited excellent storage stability.

[0181] Block copolymer No. 4 is an AB-type diblock copolymer formed by radical polymerization of a polymerizable composition (A) containing a hydroxyl group-containing (meth)acrylate (a-1) and / or an alkoxy group-containing (meth)acrylate (a-2) in block A, and by radical polymerization of a polymerizable composition (B) containing a nitrogen-containing functional group-containing vinyl monomer (b-1) in block B. Colored composition No. 4 using this block copolymer No. 4 as a dispersant has a low initial viscosity but a high viscosity after storage, and does not have curability.

[0182] Block copolymer No. 5 is an AB-type diblock copolymer formed by radical polymerization of a polymerizable composition containing a hydroxyl group-containing (meth)acrylate (a-1) and a vinyl monomer (c-1) having an (meth)acryloyl group and an ethylenically unsaturated group other than the (meth)acryloyl group in one molecule, with Block A being formed by radical polymerization of a polymerizable composition (B) containing a nitrogen-containing functional group-containing vinyl monomer (b-1). Colored composition No. 5 using this block copolymer No. 5 as a dispersant had high initial viscosity and poor dispersion performance of the coloring agent.

[0183] Block copolymer No. 7 is formed by radical polymerization of a polymerizable composition (A) containing a (meth)acrylate (a-1) having a hydroxyl group and / or a (meth)acrylate (a-2) having an alkoxy group for block A, and by radical polymerization of a polymerizable composition (B) containing a vinyl monomer (b-1) having a nitrogen-containing functional group for block B. Block C is formed by radical polymerization of a polymerizable composition that does not contain a vinyl monomer (c-1) having an (meth)acryloyl group and an ethylenically unsaturated group other than a (meth)acryloyl group in one molecule, and an ethylenically unsaturated group is introduced after polymerization. Colored composition No. 7 using this block copolymer No. 7 as a dispersant gelled during preparation.

[0184] The present invention includes the following embodiments.

[0185] (Aspect 1) An ABC-type triblock copolymer having A block, B block and C block, wherein A block, B block and C block are formed by radical polymerization of polymerizable composition (A), polymerizable composition (B), or polymerizable composition (C), respectively, wherein polymerizable composition (A) contains a (meth)acrylate (a-1) having a hydroxyl group and / or a (meth)acrylate (a-2) having an alkoxy group, wherein polymerizable composition (B) contains a vinyl monomer (b-1) having a nitrogen-containing functional group, and polymerizable composition (C) contains a vinyl monomer (c-1) having a (meth)acryloyl group and an ethylenically unsaturated group other than a (meth)acryloyl group in one molecule, The block copolymer is characterized in that the vinyl monomer (c-1) is a structural unit derived from vinyl monomer (c-1) and having an ethylenically unsaturated group other than a (meth)acryloyl group, and the molar volume ratio (X / Y) of the structural unit (Y) derived from vinyl monomer (b-1) is 0.1 to 1.1.

[0186] (Aspect 2) The block copolymer according to aspect 1, wherein the double bond equivalent of the block copolymer is 300 to 6,000.

[0187] (Aspect 3) The block copolymer according to aspect 1 or 2, wherein the vinyl monomer (c-1) is a compound represented by formula (5).

[0188] [In equation (5), R 51 R represents a hydrogen atom or a methyl group. 52 R represents a single bond or a saturated hydrocarbon group having 1 to 10 carbon atoms. 53 [This represents a hydrogen atom or a methyl group.]

[0189] (Aspect 4) The block copolymer according to any one of aspects 1 to 3, wherein the content of the vinyl monomer (c-1) in 100 mol% of the monomer contained in the polymerizable composition (C) is 80 mol% or more.

[0190] (Aspect 5) The block copolymer according to any one of aspects 1 to 4, wherein the total content of (meth)acrylate (a-1) and (meth)acrylate (a-2) in 100 mol% of the monomer contained in the polymerizable composition (A) is 5 mol% to 70 mol%.

[0191] (Aspect 6) The block copolymer according to any one of aspects 1 to 5, wherein the nitrogen-containing functional group of the vinyl monomer (b-1) is a basic group.

[0192] (Aspect 7) The block copolymer according to claim 6, wherein the amine value of the block copolymer is 10 mg KOH / g to 170 mg KOH / g.

[0193] (Aspect 8) The block copolymer according to any one of aspects 1 to 7, wherein the molar ratio of the total molar amount of structural units constituting block A to the total molar amount of structural units constituting block B (block A / block B) is 0.10 to 9.00, and the molar ratio of the total molar amount of structural units constituting block C to the total molar amount of structural units constituting block B (block C / block B) is 0.10 to 9.00.

[0194] (Aspect 9) The block copolymer according to any one of aspects 1 to 8, wherein the weight-average molecular weight of the block copolymer is 5,000 to 40,000.

[0195] (Aspect 10) The block copolymer according to any one of aspects 1 to 9, wherein the radical polymerization is living radical polymerization using an organotellurium compound.

[0196] (Aspect 11) A dispersant characterized by containing a block copolymer according to any one of aspects 1 to 10.

[0197] (Aspect 12) A colored composition characterized by containing a coloring agent, a dispersion medium, and the dispersant described in Aspect 11.

[0198] (Aspect 13) The coloring composition according to aspect 12, characterized in that it is for use as a color filter.

[0199] (Aspect 14) A color filter characterized by comprising a colored layer formed using the colored composition described in Aspect 12.

[0200] (Aspect 15) A method for producing a block copolymer according to any one of aspects 1 to 9, comprising: a first step of radical polymerization of the polymerizable composition (A) to form an A block; a second step of radical polymerization of the A block with the polymerizable composition (B) to obtain an AB diblock copolymer; and a third step of radical polymerization of the AB diblock copolymer with the polymerizable composition (C) to obtain an ABC triblock copolymer.

Claims

1. An ABC-type triblock copolymer having A block, B block and C block, wherein A block, B block and C block are formed by radical polymerization of polymerizable composition (A), polymerizable composition (B), or polymerizable composition (C), respectively, wherein polymerizable composition (A) contains a (meth)acrylate (a-1) having a hydroxyl group and / or a (meth)acrylate (a-2) having an alkoxy group, wherein polymerizable composition (B) contains a vinyl monomer (b-1) having a nitrogen-containing functional group, and polymerizable composition (C) contains a vinyl monomer (c-1) having a (meth)acryloyl group and an ethylenically unsaturated group other than a (meth)acryloyl group in one molecule, The block copolymer is characterized in that the vinyl monomer (c-1) is a structural unit derived from vinyl monomer (c-1) and having an ethylenically unsaturated group other than a (meth)acryloyl group, and the molar volume ratio (X / Y) of the structural unit (Y) derived from vinyl monomer (b-1) is 0.1 to 1.

1.

2. The block copolymer according to claim 1, wherein the double bond equivalent of the block copolymer is 300 to 6,000.

3. The block copolymer according to claim 1 or 2, wherein the vinyl monomer (c-1) is a compound represented by formula (5). [In equation (5), R 51 R represents a hydrogen atom or a methyl group. 52 R represents a single bond or a saturated hydrocarbon group having 1 to 10 carbon atoms. 53 [This represents a hydrogen atom or a methyl group.] 4. The block copolymer according to claim 1 or 2, wherein the content of the vinyl monomer (c-1) in 100 mol% of the monomer contained in the polymerizable composition (C) is 80 mol% or more.

5. The block copolymer according to claim 1 or 2, wherein the total content of (meth)acrylate (a-1) and (meth)acrylate (a-2) in 100 mol% of the monomer contained in the polymerizable composition (A) is 5 mol% to 70 mol%.

6. The block copolymer according to claim 1 or 2, wherein the nitrogen-containing functional group of the vinyl monomer (b-1) is a basic group.

7. The block copolymer according to claim 6, wherein the amine value of the block copolymer is 10 mg KOH / g to 170 mg KOH / g.

8. The block copolymer according to claim 1 or 2, wherein the molar ratio of the total molar amount of structural units constituting block A to the total molar amount of structural units constituting block B (block A / block B) is 0.10 to 9.00, and the molar ratio of the total molar amount of structural units constituting block C to the total molar amount of structural units constituting block B (block C / block B) is 0.10 to 9.

00.

9. The block copolymer according to claim 1 or 2, wherein the weight-average molecular weight of the block copolymer is 5,000 to 40,000.

10. The block copolymer according to claim 1 or 2, wherein the radical polymerization is living radical polymerization using an organotellurium compound.

11. A dispersant characterized by containing the block copolymer described in claim 1 or 2.

12. A colored composition characterized by containing a coloring agent, a dispersion medium, and the dispersant described in claim 11.

13. The coloring composition according to claim 12, characterized in that it is for use as a color filter.

14. A color filter characterized by comprising a colored layer formed using the colored composition described in claim 12.

15. A method for producing a block copolymer according to claim 1 or claim 2, comprising: a first step of radical polymerization of the polymerizable composition (A) to form an A block; a second step of radical polymerization of the polymerizable composition (B) onto the A block to obtain an AB diblock copolymer; and a third step of radical polymerization of the polymerizable composition (C) onto the AB diblock copolymer to obtain an ABC triblock copolymer.

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