Block copolymer, dispersant, and coloring composition

Abstract

[Problem] To provide a block copolymer which has high dispersibility of a coloring material when used as a dispersant for a coloring composition. [Solution] A block copolymer characterized by having a block A that does not substantially contain a structural unit (b-2) having a basic group, and a block B that contains a structural unit (b-1) having a hydroxyl group and a structural unit (b-2) having a basic group, and the molar ratio of the structural unit (b-1) to the structural unit (b-2) in the B segment ((b-1) / (b-2)) is 5 / 95-95 / 5.

Description

Technical Field

[0001] The present invention relates to a block copolymer, and more particularly to a block copolymer that can be used as a dispersant for a coloring material of a coloring composition. Background Art

[0002] In the past, in the preparation of color filters used in liquid crystal displays, etc., methods for imparting coloring materials to substrates are known to include dyeing, printing, inkjet, electrodeposition, pigment dispersion, etc. Among them, the pigment dispersion method has become the mainstream from the perspectives of spectral characteristics, durability, pattern shape and precision. In the pigment dispersion method, a coating film formed by a coloring composition mixed with a pigment, a dispersant, a dispersion medium (solvent), a binder resin, etc. is formed on a substrate, and a radiation is irradiated through a photomask of a desired pattern shape to cure, and alkali development is performed.

[0003] In recent years, in order to obtain good color reproducibility and high contrast of color filters, the high concentration of pigments in coloring compositions has been studied. When the pigment is highly concentrated, the proportion of the dispersant is relatively reduced, so the dispersant is required to have high dispersibility (for example, refer to paragraph 0004 of patent document 1). In addition, in alkali development, the binder resin with alkali solubility plays a great role. However, in the case of a pigment dispersion composition in which the pigment is highly concentrated, the proportion of the binder resin as a developing component is reduced, and the alkali developability decreases. Therefore, the dispersant is also required to have the alkali developability originally required for the binder resin. As such a dispersant, Patent Document 2 records the use of an AB block copolymer as a pigment dispersion, wherein the AB block copolymer is composed of an A block having a polylactone chain in the side chain and a B block having a tertiary amine group in the side chain (refer to paragraphs 0023 to 0045 of Patent Document 2).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2009-265515

[0007] Patent Document 2: Japanese Patent Application Publication No. 2013-119568 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] In order to improve the dispersibility of the coloring material, it has been proposed to introduce a tertiary amine group into the side chain of a resin-type dispersant (see Patent Document 2). However, due to the high concentration of the coloring material in the coloring composition in recent years, further improvement of the dispersibility is required.

[0010] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a block copolymer having high dispersibility of a coloring material when used as a dispersant for a coloring composition.

[0011] Solutions to the problem

[0012] The block copolymer of the present invention which can solve the above-mentioned problems is a block copolymer having an A segment and a B segment, characterized in that the A segment substantially does not contain a structural unit (b-2) having a basic group, the B segment contains a structural unit (b-1) having a hydroxyl group and a structural unit (b-2) having a basic group, and the molar ratio ((b-1) / (b-2)) of the structural unit (b-1) to the structural unit (b-2) in the B segment is 5 / 95 to 95 / 5.

[0013] The block copolymer of the present invention is designed to have a high affinity between the A segment and the solvent, a high affinity between the B segment and the coloring material, and a basic group introduced in the B segment adsorbs on the coloring material. Here, it is believed that by copolymerizing the structural unit (b-1) having a hydroxyl group that easily interacts with the solvent on the B segment, the affinity of the adsorption site and the dispersion medium is improved. Therefore, it is believed that by controlling the molar ratio ((b-1) / (b-2)) of the structural unit (b-1) and the structural unit (b-2) in the B segment within a specified range, while maintaining the affinity of the B segment for the coloring material, the affinity with the dispersion medium can also be improved, and the performance of the block copolymer in dispersing the coloring material can be further improved.

[0014] Effects of the Invention

[0015] The block copolymer of the present invention is excellent in the ability to disperse a coloring material, and when used as a dispersant for a coloring material, a coloring composition having excellent viscosity stability can be obtained. DETAILED DESCRIPTION

[0016] An example of a preferred embodiment of the present invention will be described below. However, the following embodiments are merely illustrative and the present invention is not limited to the following embodiments.

[0017] <Block copolymer>

[0018] The block copolymer of the present invention has an A segment and a B segment. In the present specification, "A segment" refers to a portion consisting of the "A block" in the copolymer, and "B segment" refers to a portion consisting of the "B block" in the copolymer. In the present specification, "vinyl monomer" refers to a monomer having a carbon-carbon double bond that can be subjected to free radical polymerization in the molecule, "structural unit derived from a vinyl monomer" refers to a structural unit in which the carbon-carbon double bond that can be subjected to free radical polymerization of the vinyl monomer is polymerized to form a carbon-carbon single bond, "(meth)acrylic group" refers to "at least one of acrylic group and methacrylic group", "(meth)acrylate" refers to "at least one of acrylic ester and methacrylate", "(meth)acrylate" refers to "ester compound in which the hydrogen atom of the carboxyl group possessed by (meth)acrylic acid is substituted by an organic group", "(meth)acryloyl" refers to "at least one of acryloyl and methacryloyl", "(meth)acrylic monomer" refers to "monomer having a (meth)acrylic group in the molecule", and also includes "(meth)acrylate", and "vinyl monomer" also includes "(meth)acrylate" and "(meth)acrylic monomer".

[0019] In this specification, "X to Y" (X and Y are arbitrary numbers) means "X or more and Y or less". In addition, "X or more" (X is an arbitrary number) includes the meaning of "X or more than X", and "Y or less" (Y is an arbitrary number) also includes the meaning of "Y or less than Y".

[0020] Furthermore, “X and / or Y (X and Y are arbitrary structures)” means “at least one of X and Y” and has three meanings of “only X”, “only Y”, and “X and Y”.

[0021] (A segment)

[0022] The A segment refers to a portion consisting of an A block in a block copolymer. The block copolymer may have only one A block as the A segment, or may have multiple A blocks as the A segment. When the A segment has multiple A blocks, these A blocks may be of the same composition or of different compositions. The A segment does not substantially contain a structural unit (b-2) having a basic group.

[0023] The A block is a block that does not substantially contain a structural unit (b-2) having a basic group. As the structural unit constituting the A block, there can be cited a structural unit derived from a (meth) acrylic monomer and a structural unit derived from a vinyl monomer other than a (meth) acrylic monomer. The structural unit constituting the A block may be only one type or may have two or more types. In the case where the A block contains two or more structural units, the various structural units contained in the A block may be contained in the A block in any manner such as random copolymerization, block copolymerization, etc., and from the viewpoint of uniformity, it is preferably contained in the form of random copolymerization.

[0024] Examples of the (meth)acrylic monomer that forms the structural unit derived from the (meth)acrylic monomer include a (meth)acrylic monomer having a chain alkyl group, a (meth)acrylic monomer having a cyclic alkyl group, a (meth)acrylic monomer having an aromatic group, a (meth)acrylic monomer having a hydroxyl group, a (meth)acrylic monomer having an alkoxy group, a (meth)acrylic monomer having an oxygen-containing heterocyclic group, a (meth)acrylic monomer having an amide group, and a (meth)acrylic monomer having an acidic group.

[0025] Examples of the (meth)acrylic monomer having a chain alkyl group include (meth)acrylates having a linear alkyl group and (meth)acrylates having a branched alkyl group.

[0026] As the (meth)acrylate having a linear alkyl group, a (meth)acrylate having a linear alkyl group with carbon atoms of 1 to 20 is preferred, and a (meth)acrylate having a linear alkyl group with carbon atoms of 1 to 10 is more preferred. Specific examples of the (meth)acrylate having a linear alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-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-stearoyl (meth)acrylate.

[0027] As the (meth)acrylate having a branched alkyl group, a (meth)acrylate having a branched alkyl group with a carbon number of 3 to 20 is preferred, and a (meth)acrylate having a branched alkyl group with a carbon number of 3 to 10 is preferred. Specific examples of the (meth)acrylate having a branched alkyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, and the like.

[0028] Examples of the (meth)acrylic monomer having a cyclic alkyl group include (meth)acrylates having a cyclic alkyl group having a monocyclic structure and (meth)acrylates having a cyclic alkyl group having a bridged ring structure.

[0029] As the (meth)acrylate having a cyclic alkyl group with a monocyclic structure, preferably a (meth)acrylate having a cyclic alkyl group with a monocyclic structure having 6 to 12 carbon atoms. Specific examples of the (meth)acrylate having a cyclic alkyl group with a monocyclic structure include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, and the like.

[0030] As the (meth)acrylate having a cyclic alkyl group with a bridged ring structure, a (meth)acrylate having a bridged ring structure having carbon atoms of 6 to 12 is preferred. Specific examples of the (meth)acrylate having a cyclic alkyl group with a bridged ring structure include isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate.

[0031] As the (meth)acrylic monomer having an aromatic group, a (meth)acrylate having an aromatic group in which the number of carbon atoms of the aromatic group is 6 to 12 is preferred. The aromatic group may have a chain portion such as an alkylaryl group, an aralkyl group, an aryloxyalkyl group, etc. Specific examples of the (meth)acrylate having an aromatic group include benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc.

[0032] Examples of the (meth)acrylic monomer having a hydroxyl group include (meth)acrylates having a hydroxyalkyl group, (meth)acrylates having a lactone-modified hydroxyl group, and (meth)acrylates having a polyalkylene glycol group.

[0033] Specific examples of the (meth)acrylate having a 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, 12-hydroxylauryl (meth)acrylate, etc. The hydroxyalkyl group is preferably a straight chain or a branched chain. In addition, the number of carbon atoms of the hydroxyalkyl group is preferably 1 to 10, and more preferably 1 to 5.

[0034] As specific examples of the (meth)acrylate having a lactone-modified hydroxyl group, there can be cited substances obtained by adding lactone to the above-mentioned (meth)acrylate having a hydroxyalkyl group, preferably substances obtained by adding caprolactone. The amount of caprolactone added is preferably 1 mol to 20 mol, more preferably 1 mol to 10 mol. As the (meth)acrylate having a lactone-modified hydroxyl group, preferably 1 mol of caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 2 mol of caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 3 mol of caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 4 mol of caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 5 mol of caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 10 mol of caprolactone adduct of 2-hydroxyethyl (meth)acrylate, etc.

[0035] Specific examples of the (meth)acrylate having a polyalkylene glycol group include terminal hydroxyl polyethylene glycol (polymerization degree = 2 to 10) mono(meth)acrylate and terminal hydroxyl polypropylene glycol (polymerization degree = 2 to 10) mono(meth)acrylate.

[0036] Examples of the (meth)acrylic monomer having an alkoxy group include (meth)acrylates having an alkoxyalkyl group and (meth)acrylates having an alkoxypolyalkylene glycol group.

[0037] Specific examples of the (meth)acrylate having an alkoxyalkyl group include methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate.

[0038] Specific examples of the (meth)acrylate having an alkoxypolyalkylene glycol group include (meth)acrylates having a polyethylene glycol structure such as polyethylene glycol (degree of polymerization = 2 to 10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization = 2 to 10) ethyl ether (meth)acrylate, polyethylene glycol (degree of polymerization = 2 to 10) propyl ether (meth)acrylate; and (meth)acrylates having a polypropylene glycol structural unit such as polypropylene glycol (degree of polymerization = 2 to 10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization = 2 to 10) ethyl ether (meth)acrylate, polypropylene glycol (degree of polymerization = 2 to 10) propyl ether (meth)acrylate.

[0039] As the (meth)acrylic monomer having an oxygen-containing heterocyclic group, a (meth)acrylate having a four-membered ring to a six-membered ring oxygen-containing heterocyclic group is preferred. Specific examples of (meth)acrylate having an oxygen-containing heterocyclic group include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (3-ethyloxetane-3-yl)methyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, and 2-[(2-tetrahydropyranyl)oxy)]ethyl (meth)acrylate.

[0040] Specific examples of the (meth)acrylic acid-based monomer having an amide group include N,N-dimethyl(meth)acrylamide and 4-(meth)acryloylmorpholine.

[0041] Examples of the acidic group of the (meth) acrylic monomer having an acidic group include carboxyl (-COOH), sulfonic acid (-SO3H), phosphoric acid (-OPO3H2), phosphonic acid (-PO3H2), and phosphinic acid (-PO2H2). Examples of the (meth) acrylic monomer having an acidic group include (meth) acrylic acid, (meth) acrylic ester having a carboxyl group, (meth) acrylic ester having a phosphoric acid group, and (meth) acrylic ester having a sulfonic acid group, preferably (meth) acrylic acid and (meth) acrylic ester having a carboxyl group.

[0042] Specific examples of (meth)acrylates having a carboxyl group include carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, monomers obtained by reacting anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride, and the like with (meth)acrylates having a hydroxyalkyl group, and the like, such as 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, and 2-(meth)acryloyloxyethyl phthalate. Specific examples of (meth)acrylates having a phosphoric acid group include 2-(phosphoryloxy)ethyl (meth)acrylate, and the like. Specific examples of (meth)acrylates having a sulfonic acid group include ethyl (meth)acrylate sulfonate, and the like.

[0043] The structural unit derived from a vinyl monomer other than the (meth)acrylic acid group monomer is not particularly limited as long as it is a structural unit composed of a vinyl monomer copolymerizable with both the (meth)acrylic acid group monomer and a vinyl monomer forming the B block described later.

[0044] Specific examples of the vinyl monomers forming the structural units derived from the vinyl monomers other than the (meth)acrylic monomers include α-olefins, styrene monomers, hydroxyl-containing vinyl monomers, heterocyclic vinyl monomers, vinyl amides, carboxylic acid vinyl esters, dienes, etc. These vinyl monomers may also have hydroxyl groups or epoxy groups.

[0045] Examples of the α-olefin include 1-hexene, 1-octene, and 1-decene.

[0046] The styrene monomers may include substituted or unsubstituted styrenes. As substituents that may be substituted on styrene, alkyl, aryl, alkoxy, aryloxy, etc. may be mentioned. In addition, styrene monomers also include condensed ring compounds having two or more benzene rings. Specific examples of the styrene vinyl monomers include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 2,4-dimethylstyrene, 4-methoxystyrene, 4-phenylstyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene, etc.

[0047] Examples of the hydroxyl group-containing vinyl monomer include 4-vinylphenol and 4-hydroxybutyl vinyl ether.

[0048] Examples of the heterocyclic ring-containing vinyl monomer include 2-vinylthiophene, N-methyl-2-vinylpyrrole, and 1-vinyl-2-pyrrolidone.

[0049] Examples of the vinyl amide include N-vinylformamide, N-vinylacetamide, and N-vinyl-ε-caprolactam.

[0050] Examples of the vinyl carboxylate include vinyl acetate, vinyl pivalate, and vinyl benzoate.

[0051] Examples of the dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, and 7-methyl-1,6-octadiene.

[0052] The A block preferably contains a structural unit derived from a (meth)acrylic acid monomer. The structural unit derived from the (meth)acrylic acid monomer may be one type or two or more types. The A block has a structural unit derived from a (meth)acrylic acid monomer, and thus has improved affinity with the dispersion medium and the binder resin added to the coloring composition.

[0053] The content of the structural unit derived from the (meth)acrylic acid group monomer in 100 mol % of the structural units constituting the A block is preferably 80 mol % or more, more preferably 90 mol % or more, further preferably 95 mol % or more, particularly preferably 100 mol %.

[0054] When the A segment has a plurality of A blocks, the content of the structural unit derived from the (meth)acrylic acid group monomer in 100 mol % of the structural units constituting the A segment is preferably 80 mol % or more, more preferably 90 mol % or more, further preferably 95 mol % or more, and particularly preferably 100 mol %.

[0055] The A segment preferably contains a structural unit derived from a (meth)acrylic monomer, wherein the (meth)acrylic monomer is at least one selected from the following monomers: a (meth)acrylic monomer having a chain alkyl group, a (meth)acrylic monomer having a cyclic alkyl group, a (meth)acrylic monomer having an aromatic group, a (meth)acrylic monomer having a hydroxyl group, a (meth)acrylic monomer having an alkoxy group, a (meth)acrylic monomer having an oxygen-containing heterocyclic group, a (meth)acrylic monomer having an amide group, and a (meth)acrylic monomer having an acidic group. By having a structural unit derived from these (meth)acrylic monomers, the affinity with the dispersion medium and the binder resin formulated in the coloring composition is further improved.

[0056] As a structural unit derived from a (meth) acrylic acid-based monomer, the A segment preferably contains at least one structural unit derived from a (meth) acrylic acid-based monomer selected from a structural unit (a-1) derived from a (meth) acrylic acid ester having a hydroxyl group and a structural unit (a-2) derived from a (meth) acrylic acid ester having an alkoxy group, more preferably contains a structural unit (a-1) derived from a (meth) acrylic acid ester having a hydroxyl group, and further preferably contains a structural unit derived from a (meth) acrylic acid ester having a lactone-modified hydroxyl group. By having a hydroxyl group or an alkoxy group in the A segment, the dispersibility of the coloring material can be further improved. Among them, the structural unit derived from a (meth) acrylic acid ester having a lactone-modified hydroxyl group has an ester bond portion and a terminal hydroxyl group in the side chain, and therefore has a high affinity with the dispersion medium and the binder resin, and can improve the re-solubility in the dispersion medium.

[0057] As the structural unit derived from the (meth)acrylate having a lactone-modified hydroxyl group, a structural unit represented by formula (4) is preferred.

[0058]

[0059] [In formula (4), n1 represents an integer of 1 to 10, R 41 represents a hydrogen atom or a methyl group, R 42 represents an alkylene group having 1 to 10 carbon atoms, R 43 represents an alkylene group having 1 to 10 carbon atoms.]

[0060] In the formula (4), n1 is preferably an integer of 1-7, and more preferably an integer of 1-5.

[0061] The R 42 The alkylene group having 1 to 10 carbon atoms represented by may be either a straight chain or a branched chain, but a straight chain is preferred. 42 Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, and 1-methylethylene. 42 An alkylene group having 1 to 5 carbon atoms is preferred.

[0062] The R 43 The alkylene group having 1 to 10 carbon atoms represented by may be either a straight chain or a branched chain, but a straight chain is preferred. 43 Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene and the like. 43 An alkylene group having 1 to 8 carbon atoms is preferred, and an alkylene group having 3 to 8 carbon atoms is more preferred.

[0063] When the A segment contains a structural unit (a-1) derived from a (meth)acrylate having a hydroxyl group and / or a structural unit (a-2) derived from a (meth)acrylate having an alkoxy group, the total content of these in 100 mol% of the structural units constituting the A segment is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more, and preferably 95 mol% or less, more preferably 70 mol% or less, and further preferably 40 mol% or less. By setting the total content of the structural unit (a-1) derived from a (meth)acrylate having a hydroxyl group and the structural unit (a-2) derived from a (meth)acrylate having an alkoxy group to the above range, the dispersibility of the coloring material can be further improved.

[0064] When the A segment contains a structural unit derived from a (meth)acrylate having a lactone-modified hydroxyl group, the content thereof is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more, in 100 mol% of the structural units constituting the A segment, and preferably 95 mol% or less, more preferably 70 mol% or less, and further preferably 40 mol% or less. By setting the content of the structural unit derived from the (meth)acrylate having a lactone-modified hydroxyl group within the above range, the re-solubility of the coloring composition containing the block copolymer can be improved.

[0065] The A segment may also have a structural unit from a vinyl monomer having an acidic group (preferably a (meth) acrylic monomer having an acidic group, more preferably (meth) acrylic acid). By having a structural unit from a vinyl monomer having an acidic group, the solubility in the alkaline developer is increased, and the alkaline developability of the coloring composition can be improved. However, if the proportion thereof increases, the affinity with the dispersion medium and the binder resin may decrease. Therefore, the proportion of the structural unit from the vinyl monomer having an acidic group is preferably set according to the ratio of the acid value of the block copolymer as a whole being lower than the amine value.

[0066] When the structural unit derived from the vinyl monomer having an acidic group is contained, the content thereof is preferably 2 mol% or more and preferably 20 mol% or less in 100 mol% of the structural units constituting the A segment. If the content of the structural unit derived from the vinyl monomer having an acidic group is 2 mol% or more, the dissolution rate during neutralization with an alkali in alkali development is accelerated, and if it is 20 mol% or less, the hydrophilicity is not too high, and the formed pixels can be prevented from becoming disordered.

[0067] The A segment does not substantially contain a structural unit (b-2) having a basic group. That is, the monomers constituting the A segment preferably do not contain a monomer having a basic group. If there is a basic group in the A segment, when used as a dispersant, the coloring material is adsorbed on both the A segment and the B segment, and the dispersibility of the coloring material decreases. The content of the structural unit (b-2) having a basic group in 100 mol% of the structural units constituting the A segment is preferably 0.5 mol% or less, more preferably 0.1 mol% or less, further preferably 0.05 mol% or less, and particularly preferably 0 mol%.

[0068] (B segment)

[0069] The B segment refers to a portion composed of a B block in a block copolymer. The block copolymer may have only one B block as the B segment, or may have a plurality of B blocks as the B segment. When the B segment has a plurality of B blocks, these B blocks may have the same composition or different compositions.

[0070] The B segment contains a structural unit (b-1) having a hydroxyl group and a structural unit (b-2) having a basic group. As the B segment, the following modes can be cited: a mode containing a B block, wherein the B block contains a structural unit (b-1) having a hydroxyl group and a structural unit (b-2) having a basic group; a mode containing a B1 block and a B2 block, wherein the B1 block contains a structural unit (b-1) having a hydroxyl group and a structural unit (b-2) having a basic group, and the B2 block contains a structural unit (b-2) having a basic group; a mode containing a B1 block and a B2 block, wherein the B1 block contains a structural unit (b-1) having a hydroxyl group and a structural unit (b-2) having a basic group, and the B2 block contains a structural unit (b-1) having a hydroxyl group and a structural unit (b-2) having a basic group.

[0071] The B block is a block containing a structural unit (b-1) having a hydroxyl group and a structural unit (b-2) having a basic group, or a block containing no structural unit (b-1) having a hydroxyl group but containing a structural unit (b-2) having a basic group. The various structural units contained in the B block may be contained in the B block in any form such as random copolymerization or block copolymerization, but are preferably contained in the form of random copolymerization from the viewpoint of uniformity.

[0072] (Structural unit (b-1) having a hydroxyl group)

[0073] At least one block of the B block contains a structural unit (b-1) having a hydroxyl group. By containing the structural unit (b-1) in at least one of the B blocks, the affinity for the dispersion medium can be improved. The structural unit (b-1) may be only one type or may have two or more types. It should be noted that the structural unit (b-2) having a basic group described later is not included in the structural unit (b-1) having a hydroxyl group.

[0074] Examples of the structural unit (b-1) include structures derived from a vinyl monomer having a hydroxyl group. The structural unit (b-1) having a hydroxyl group is preferably a structural unit represented by formula (1).

[0075]

[0076] [In formula (1), R 11 A represents a hydrogen atom or a methyl group. 11 represents an ester group, an amide group or a single bond, R 12 Represents a divalent hydrocarbon group, -R 13 -(OCO-R 14 ) m -base or -R 15 -(OR 16 ) n-Base, R 13 ~R 16 Each independently represents a divalent hydrocarbon group, m represents an integer of 1 to 10, and n represents an integer of 1 to 10.]

[0077] The A 11 represents an ester group (-CO-O-), an amide group (-CO-NH-) or a single bond. From the perspective of affinity for the dispersion medium and alkali developability, an ester group or an amide group is preferred. It should be noted that the bonding direction of the ester group or the amide group is not particularly limited. Examples of the bonding mode of the ester group include C-CO-OR 12 or CO-CO-R 12 , preferably C-CO-OR 12 The bonding form of the amide group can be C-CO-NH-R 12 or C-NH-CO-R 12 , preferably C-CO-NH-R 12 .

[0078] As the R 12 Examples of the divalent hydrocarbon group represented by include a linear alkylene group, a branched alkylene group, a cyclic alkylene group, and an aromatic hydrocarbon diyl group. A linear alkylene group and a branched alkylene group are preferred.

[0079] The linear alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms. Examples of the linear alkylene group include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, and dodecamethylene.

[0080] The branched alkylene group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 10 carbon atoms. Examples of the branched alkylene group include 1,2-propylene group, propylidene group, 1,2-butanediyl group, and 1,3-butanediyl group.

[0081] The cyclic alkylene group preferably has a carbon number of 6 to 12. Examples of the cyclic alkylene group include cyclopropylene group, cyclobutylene group, cyclopentylene group, and cyclohexylene group.

[0082] The arene diyl group preferably has 6 to 12 carbon atoms, and more preferably has 6 to 9 carbon atoms. Examples of the arene diyl group include phenylene and the like.

[0083] The R 12 -R 13 -(OCO-R 14 ) m -Base R13 and R 14 Each independently represents a divalent hydrocarbon group. m represents an integer of 1-10, preferably an integer of 1-7, and more preferably an integer of 1-5.

[0084] As the R 13 The divalent hydrocarbon group may be a straight chain alkylene group, a branched chain alkylene group, etc., preferably a straight chain alkylene group. The straight chain alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The branched chain alkylene group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. 13 Specific examples of include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, and 1-methylethylene.

[0085] As the R 14 The divalent hydrocarbon group may be a straight chain alkylene group, a branched chain alkylene group, etc., preferably a straight chain alkylene group. The straight chain alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and further preferably 3 to 8 carbon atoms. The branched chain alkylene group preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. 14 Specific examples of include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene and the like.

[0086] The R 12 -R 15 -(OR 16 ) n -Base R 15 and R 16 Each independently represents a divalent hydrocarbon group. n represents an integer of 1-10.

[0087] As the R 15 The divalent hydrocarbon group may be a straight chain alkylene group, a branched chain alkylene group, etc., preferably a straight chain alkylene group. The straight chain alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. The branched chain alkylene group preferably has 3 to 5 carbon atoms. 15 Specific examples of include methylene, ethylene, and 1,2-propylene.

[0088] As the R 16 The divalent hydrocarbon group may be a straight chain alkylene group, a branched chain alkylene group, etc., preferably a branched chain alkylene group. The straight chain alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. The branched chain alkylene group preferably has 3 to 5 carbon atoms. 16Specific examples of include methylene, ethylene, and 1,2-propylene.

[0089] Specific examples of the vinyl monomer forming the structural unit represented by formula (1) include preferably (meth)acrylates having a hydroxyalkyl group, (meth)acrylates having a lactone-modified hydroxyl group, (meth)acrylates having a polyalkylene glycol group, and vinyl monomers having a hydroxyl group.

[0090] Examples of the (meth)acrylate having a 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, 12-hydroxylauryl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.

[0091] Examples of the (meth)acrylate having a lactone-modified hydroxyl group include 1 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 2 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 3 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 4 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 5 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, and 10 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate.

[0092] Examples of the (meth)acrylate having a polyalkylene glycol group include terminal hydroxyl polyethylene glycol (polymerization degree = 2 to 10) mono(meth)acrylate and terminal hydroxyl polypropylene glycol (polymerization degree = 2 to 10) mono(meth)acrylate.

[0093] Examples of the hydroxyl group-containing vinyl monomer include 4-vinylphenol and 4-hydroxybutyl vinyl ether.

[0094] In 100 mol% of the structural units constituting the B segment, the content of the structural unit (b-1) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 65 mol% or less. If the content of the structural unit (b-1) is within the above range, the B segment is considered to have a high affinity with the coloring material.

[0095] In the B block containing the structural unit (b-1), the content of the structural unit (b-1) in 100 mol% of the structural units constituting the B block is preferably greater than 0 mol%, more preferably greater than 1 mol%, further preferably greater than 10 mol%, preferably less than 99 mol%, more preferably less than 80 mol%, further preferably less than 65 mol%.

[0096] (Structural unit having a basic group (b-2))

[0097] The B block constituting the B segment contains a structural unit (b-2) having a basic group. The structural unit (b-2) provides high adsorption performance for coloring materials. The structural unit (b-2) may be one type or two or more types.

[0098] The basic group is a group showing alkalinity, and amino is preferred from the perspective of ease of raw material acquisition and synthesis. In this specification, amino includes not only general amino (-NH2) but also -NHR where H is substituted by a hydrocarbon group. a 、-NR a R b (R a , R b Each independently represents a chain or cyclic hydrocarbon group, and R a and R b They may be bonded to each other to form a ring structure. ) and substituted amino groups and nitrogen-containing heterocyclic groups (pyridyl, imidazolyl, etc.) represented by the following. In addition, in this specification, hydroxyl groups are not included in the basic groups.

[0099] Examples of the structural unit (b-2) include a structure derived from a vinyl monomer having a basic group.

[0100] As the structural unit (b-2), a structural unit represented by formula (2) is preferred.

[0101]

[0102] [In formula (2), R 21 A represents a hydrogen atom or a methyl group. 21 represents an ester group, an amide group or a single bond, R 22 Represents a divalent hydrocarbon group, R 23 and R 24 Each independently represents a hydrocarbon group which may contain a heteroatom, R 23 and R 24 Can bond with each other to form a ring structure.]

[0103] The A 21represents an ester group (-CO-O-), an amide group (-CO-NH-) or a single bond. From the perspective of affinity for the dispersion medium and alkali developability, an ester group or an amide group is preferred. It should be noted that the bonding direction of the ester group or the amide group is not particularly limited. Examples of the bonding mode of the ester group include C-CO-OR 22 or CO-CO-R 22 , preferably C-CO-OR 22 The bonding form of the amide group can be C-CO-NH-R 22 or C-NH-CO-R 22 , preferably C-CO-NH-R 22 .

[0104] As the R 22 Examples of the divalent hydrocarbon group represented by include a linear alkylene group, a branched alkylene group, a cyclic alkylene group, an alkenylene group, and an aromatic hydrocarbon diyl group, and a linear alkylene group is preferred.

[0105] The linear alkylene group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms. Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.

[0106] The branched alkylene group preferably has a carbon number of 3 to 10. Examples of the branched alkylene group include 1,2-propylene group, propylidene group, 1,2-butanediyl group, and 1,3-butanediyl group.

[0107] The cyclic alkylene group preferably has a carbon number of 6 to 12. Examples of the cyclic alkylene group include cyclopropylene group, cyclobutylene group, cyclopentylene group, and cyclohexylene group.

[0108] The alkenylene group preferably has a carbon number of 2 to 10. Examples of the alkenylene group include vinylene, 2-propenylene, 2-butenylene, and 3-butenylene.

[0109] The arene diyl group preferably has a carbon number of 6 to 12. Examples of the arene diyl group include a phenylene group and the like.

[0110] Specific examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a trimethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a dodecamethylene group, and the like.

[0111] As the R 23 and R 24 The hydrocarbon group which may contain a hetero atom in includes a chain hydrocarbon group and a cyclic hydrocarbon group, and a chain hydrocarbon group is preferred.

[0112] Examples of the chain hydrocarbon group include a linear alkyl group and a branched alkyl group, and a linear alkyl group is preferred.

[0113] The number of carbon atoms of the linear alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5. Examples of the linear alkyl group include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-nonyl, n-decyl, and n-lauryl.

[0114] The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 3 to 5 carbon atoms. Examples of the branched alkyl group include isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, neopentyl, and isooctyl.

[0115] Examples of the cyclic hydrocarbon group include a cyclic alkyl group and an aromatic group. The cyclic alkyl group and the aromatic group may have a chain portion.

[0116] The number of carbon atoms in the cyclic alkyl group is preferably 4 to 18, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the cyclic alkyl group include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0117] The number of carbon atoms in the aromatic group is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6 to 8. Examples of the aromatic group include phenyl, tolyl, xylyl, and mesityl.

[0118] Examples of the chain portion of the cyclic alkyl group having a chain portion and the chain portion of the aromatic group having a chain portion include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms.

[0119] The hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the hydrocarbon group is substituted with a hetero atom. Examples of the hetero atom that the hydrocarbon group may contain include an oxygen atom and the like.

[0120] Furthermore, the hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms.

[0121] R 23 and R 24 Bonding to form a ring structure refers to R 23 and R 24 A cyclic structure is formed via a nitrogen atom. As the cyclic structure, for example, a five-membered to seven-membered nitrogen-containing heterocyclic ring or a condensed ring formed by condensing two nitrogen-containing heterocyclic rings thereof can be cited. The nitrogen-containing heterocyclic ring is preferably non-aromatic, and a saturated ring is more preferred. Specifically, the structures represented by the following formulas (2-1), (2-2), and (2-3) can be cited.

[0122]

[0123] [In formula (2-1), (2-2), and (2-3), R 25 represents an alkyl group having 1 to 6 carbon atoms, l represents an integer of 0 to 5, m represents an integer of 0 to 4, n represents an integer of 0 to 4, and * represents a bonding site. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R 25 They may be the same or different.]

[0124] Specific examples of the vinyl monomer that forms the structural unit represented by formula (2) 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.

[0125] The hydrogen bonding force component (δ h1 ) and the hydrogen bonding force component (δ h2 ) h1 -δ h2 ) preferably 0.5J 1 / 2 cm 1 / 2 ·mol -1 More than 2.5J is more preferred 1 / 2 cm 1 / 2 ·mol -1 Above, more preferably 5.0J 1 / 2 cm 1 / 2 ·mol -1 Above, preferably 15.0J 1 / 2 cm 1 / 2 ·mol -1 Below, more preferably 13.0J 1 / 2 cm 1 / 2 ·mol -1 Below, more preferably 10.0 J 1 / 2 cm 1 / 2 ·mol -1 Below, particularly preferably 8.0 J 1 / 2 cm 1 / 2 ·mol -1 Below. Difference (δ h1 -δ h2)If 0.5J 1 / 2 cm 1 / 2 ·mol -1 Above, it is believed that in addition to the effect of improving the adsorption of the coloring material, the effect of improving the affinity for the dispersion medium is further improved. 1 / 2 cm 1 / 2 ·mol -1 Then, it can be expected that the storage stability can be improved without inhibiting the adsorption of the structural unit (b-2) of the block copolymer and the coloring material.

[0126] When the B segment has a plurality of structural units (b-1) and / or structural units (b-2), the average value of the hydrogen bonding force components of each is obtained, and the difference (δ h1 -δ h2 ). The average value of the hydrogen bonding force component is obtained as follows: the hydrogen bonding force component of each structural unit is calculated, multiplied by the molar fraction of each structural unit, and then added. For example, when structural units (b-11) and (b-12) are contained as structural units (b-1), the average value of the hydrogen bonding force component of structural unit (b-1) is the sum of the product of the molar fraction of structural unit (b-11) in the total structural units (b-1) and the hydrogen bonding force component of structural unit (b-11) and the product of the molar fraction of structural unit (b-12) in the total structural units (b-1) and the hydrogen bonding force component of structural unit (b-12).

[0127] (Hansen Solubility Parameter)

[0128] The Hansen solubility parameter (HSP) is a value used to predict the solubility of a substance calculated by the method proposed by Hansen et al. Specifically, the HSP is a value calculated by the following formula (Mathematical formula (1)). In mathematical formula (1), δ represents the HSP of the polymer block, δ d represents the London dispersion force component of HSP, δ p represents the dipole force component of HSP, δ h represents the hydrogen bonding component of HSP.

[0129] δ 2 =δ d 2 +δ p 2 +δ h 2 (1)

[0130] The δ d , δ p and δ his the molar attraction multiplier (F) of the atomic group i constituting the structural unit of the polymer block. di , F pi , E hi ) and molar volume V i And the value is calculated by the following formula (Mathematical formula (2) to (4)).

[0131] δ d =ΣF di / ΣV i (2)

[0132] δ p =(ΣF pi 2 ) 1 / 2 / ΣV i (3)

[0133] δ h =(ΣE hi / ΣV i ) 1 / 2 (4)

[0134] The molar gravitational multiplier (F di , F pi , E hi ) and molar volume V i As shown in Table 1.

[0135] Table 1

[0136]

[0137] In addition, the content of the structural unit (b-2) in 100 mol% of the structural units constituting the B segment is preferably 5 mol% or more, more preferably 15 mol% or more, and further preferably 30 mol% or more, and preferably 90 mol% or less, more preferably 85 mol% or less, and further preferably 80 mol% or less. When the content of the structural unit (b-2) is within the above range, the adsorption capacity for the coloring material is further improved.

[0138] The content of the structural unit (b-2) in 100 mol% of the structural units constituting the B block is preferably 1 mol% or more, more preferably 50 mol% or more, and further preferably 65 mol% or more, and is preferably less than 100 mol%, more preferably 99 mol% or less, and further preferably 90 mol% or less. When the content of the structural unit (b-2) is within the above range, the adsorption capacity with the coloring material is further improved.

[0139] The molar ratio ((b-1) / (b-2)) of the structural unit (b-1) to the structural unit (b-2) in the B segment is preferably 5 / 95 or more, more preferably 10 / 90 or more, further preferably 20 / 80 or more, preferably 95 / 5 or less, more preferably 80 / 20 or less, further preferably 70 / 30 or less. When the molar ratio ((b-1) / (b-2)) is within the above range, it is considered that the adsorption of the coloring material and the affinity for the dispersion medium are more effectively exerted.

[0140] In 100 mol% of the structural units constituting the B segment, the total content ((b-1) + (b-2)) of the structural units (b-1) and (b-2) is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and preferably 100 mol% or less. If the total content ((b-1) + (b-2)) is within the above range, it can be expected that the dispersibility of the coloring material will be further improved.

[0141] (Structural unit of salt having a basic group (b-3))

[0142] The B segment may contain a salt structural unit (b-3) having a basic group in addition to the structural unit (b-1) and the structural unit (b-2). By having the structural unit (b-3), it is possible to maintain strong adsorption to the surface of the coloring material for a long time, and the storage stability is further improved. The structural unit (b-3) may be only one type, or may be two or more types.

[0143] As salts of basic groups, inorganic salts such as halide salts (F, Cl, Br, I, etc.) and sulfates of basic groups can be cited; sulfonates, sulfates, phosphates or carboxylates of organic compounds, etc. It should be noted that as salts of basic groups, amino salts are preferred from the perspective of ease of raw material acquisition and synthesis. It should be noted that in this specification, amino salts also include quaternary ammonium groups (-NR c R d R e (R c , R d and R e Each independently represents a chain or cyclic hydrocarbon group. c , R d and R e Two or more of the above may be bonded to each other to form a ring structure. )) of a salt (e.g., a halide, etc.). In addition, the structural unit (b-3) having a salt of a basic group may be a structural unit in which a part of the basic group of the structural unit (b-2) having a basic group forms a salt.

[0144] As the structural unit (b-3), a structural unit represented by formula (3) is preferred.

[0145]

[0146] [In formula (3), R 31 A represents a hydrogen atom or a methyl group. 31 represents an ester group, an amide group or a single bond, R 32 Represents a divalent hydrocarbon group, R 33 , R 34 and R 35 Each independently represents a hydrocarbon group which may contain a heteroatom, R 33 , R 34 and R 35 Two or more of them can bond to each other to form a ring structure, X - represents the counter ion.]

[0147] The A 31 represents an ester group (-CO-O-), an amide group (-CO-NH-) or a single bond. From the perspective of affinity for the dispersion medium and alkali developability, an ester group or an amide group is preferred. It should be noted that the bonding direction of the ester group or the amide group is not particularly limited. Examples of the bonding mode of the ester group include C-CO-OR 32 or CO-CO-R 32 , preferably C-CO-OR 32 The bonding form of the amide group can be C-CO-NH-R 32 or C-NH-CO-R 32 , preferably C-CO-NH-R 32 .

[0148] As the R 32 Examples of the divalent hydrocarbon group represented by include a linear alkylene group, a branched alkylene group, a cyclic alkylene group, an alkenylene group, and an aromatic hydrocarbon diyl group, and a linear alkylene group is preferred.

[0149] The linear alkylene group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms. Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.

[0150] The branched alkylene group preferably has a carbon number of 3 to 10. Examples of the branched alkylene group include 1,2-propylene group, propylidene group, 1,2-butanediyl group, and 1,3-butanediyl group.

[0151] The cyclic alkylene group preferably has a carbon number of 6 to 12. Examples of the cyclic alkylene group include cyclopropylene group, cyclobutylene group, cyclopentylene group, and cyclohexylene group.

[0152] The alkenylene group preferably has a carbon number of 2 to 10. Examples of the alkenylene group include vinylene, 2-propenylene, 2-butenylene, and 3-butenylene.

[0153] The arene diyl group preferably has a carbon number of 6 to 12. Examples of the arene diyl group include a phenylene group and the like.

[0154] Specific examples of the divalent hydrocarbon group include a methylene group, an ethylene group, an n-propylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, and an n-dodecylene group.

[0155] As the R 33 , R 34 and R 35 The hydrocarbon group which may contain a hetero atom in includes a chain hydrocarbon group and a cyclic hydrocarbon group.

[0156] Examples of the chain hydrocarbon group include a linear alkyl group and a branched alkyl group, and a linear alkyl group is preferred.

[0157] The number of carbon atoms of the linear alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5. Examples of the linear alkyl group include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-nonyl, n-decyl, and n-lauryl.

[0158] The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 3 to 5 carbon atoms. Examples of the branched alkyl group include isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, neopentyl, and isooctyl.

[0159] Examples of the cyclic hydrocarbon group include a cyclic alkyl group and an aromatic group. The cyclic alkyl group and the aromatic group may have a chain portion.

[0160] The number of carbon atoms in the cyclic alkyl group is preferably 4 to 18, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the cyclic alkyl group include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0161] The number of carbon atoms in the aromatic group is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6 to 8. Examples of the aromatic group include phenyl, tolyl, xylyl, and mesityl.

[0162] Examples of the chain portion of the cyclic alkyl group having a chain portion and the chain portion of the aromatic group having a chain portion include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms.

[0163] As the R 33 , R 34 and R 35 , preferably a combination of two straight-chain alkyl groups and one aromatic group, or all three of them are straight-chain alkyl groups.

[0164] The hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the hydrocarbon group is substituted with a hetero atom. Examples of the hetero atom that the hydrocarbon group may contain include an oxygen atom and the like.

[0165] Furthermore, the hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms.

[0166] R 33 , R 34 and R 35 Bonding to form a ring structure refers to R 33 , R 34 and R 35 Two or more of them form a cyclic structure via a nitrogen atom. As the cyclic structure, for example, a five-membered to seven-membered nitrogen-containing heterocyclic ring or a condensed ring formed by condensing two of its nitrogen-containing heterocyclic rings can be cited. The nitrogen-containing heterocyclic ring is preferably non-aromatic, and a saturated ring is more preferred. Specifically, the structures represented by the following formulas (3-1), (3-2), and (3-3) can be cited.

[0167]

[0168] [In formula (3-1), (3-2), (3-3), R 36 For R 33 . R 37 represents an alkyl group having 1 to 6 carbon atoms, l represents an integer of 0 to 5, m represents an integer of 0 to 4, n represents an integer of 0 to 4, and * represents a bonding site. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R 36 They may be the same or different.]

[0169] As X - Examples of the anion include halogen anions, carboxylate anions, sulfate anions, sulfonate anions, phosphate anions, and nitroxide anions.

[0170] Examples of the halogen anion include a fluoride anion, a chloride anion, a bromide anion, and an iodine anion.

[0171] Examples of the carboxylate anion include alkyl carboxylate anions such as acetate anion and propionate anion; and aromatic carboxylate anions such as benzoate anion.

[0172] Examples of the sulfate anion include alkyl sulfate anions such as methyl sulfate anion and ethyl sulfate anion; and aromatic sulfate anions such as phenyl sulfate anion and benzyl sulfate anion.

[0173] Examples of the sulfonate anion include alkylsulfonate anions such as a methanesulfonate anion and an ethanesulfonate anion; and aromaticsulfonate anions such as a benzenesulfonate anion and a toluenesulfonate anion.

[0174] Examples of the phosphate anions include alkyl phosphate anions such as methyl phosphate anion and ethyl phosphate anion; and aromatic phosphate anions such as phenyl phosphate anion and benzyl phosphate anion.

[0175] Specific examples of the vinyl monomer that forms the structural unit represented by formula (3) include (meth)acryloyloxyethyl trimethyl ammonium chloride, (meth)acryloyloxypropyl trimethyl ammonium chloride, (meth)acryloyloxybutyl trimethyl ammonium chloride, (meth)acryloyloxyethyl benzyl dimethyl ammonium chloride, (meth)acryloyloxypropyl benzyl dimethyl ammonium chloride, (meth)acryloyloxybutyl benzyl dimethyl ammonium chloride, (meth)acryloyloxyethyl benzyl diethyl ammonium chloride, (meth)acryloyloxypropyl benzyl diethyl ammonium chloride, (meth)acryloyloxybutyl benzyl diethyl ammonium chloride, (meth)acryloyloxyethyl benzyl diethyl ammonium chloride, (meth)acryloyloxypropyl benzyl diethyl ammonium chloride, (meth)acryloyloxybutyl benzyl diethyl ammonium chloride, (meth)acryloyloxyethyl benzyl diethyl ammonium bromide, (meth)acryloyloxypropyl benzyl diethyl ammonium bromide, (meth)acryloyloxybutyl benzyl diethyl ammonium bromide, (meth)acryloyloxyethyl benzyl diethyl ammonium iodide, (meth)acryloyloxypropyl Benzyldiethylammonium iodide, (meth)acryloyloxybutylbenzyldiethylammonium iodide, (meth)acryloyloxyethylbenzyldiethylammonium fluoride, (meth)acryloyloxypropylbenzyldiethylammonium fluoride, (meth)acryloyloxybutylbenzyldiethylammonium fluoride, (meth)acryloyloxyethyltrimethylammonium methylsulfate, (meth)acryloyloxypropyltrimethylammonium methylsulfate, (meth)acryloyloxybutyltrimethylammonium methylsulfate, (meth)acryloyloxyethyldimethylethylammonium ethylsulfate, (meth)acryloyloxypropyldimethylethylethylammonium ethylsulfate, (meth)acryloyloxybutyldimethylethylethylammonium ethylsulfate, (meth)acryloyloxyethyltrimethyltoluene-4-ammonium sulfonate, (meth)acryloyloxypropyltrimethyltoluene-4-ammonium sulfonate, (meth)acryloyloxybutyltrimethyltoluene-4-ammonium sulfonate, and the like.

[0176] When the structural unit (b-3) is contained, the content thereof is preferably 5 mol% or more, more preferably 30 mol% or more, and further preferably 45 mol% or more, in 100 mol% of the structural units constituting the B segment, and is preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 70 mol% or less. If the content of the structural unit (b-3) is within the above range, it is considered that the strong adsorption to the surface of the coloring material can be maintained for a long time, and the storage stability is further improved.

[0177] When the structural unit (b-3) is contained, the total content of the structural unit (b-2) and the structural unit (b-3) in 100 mol% of the structural units constituting the B segment ((b-2) + (b-3)) is preferably 5 mol% or more, more preferably 30 mol% or more, and further preferably 45 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 70 mol% or less. If the total content ((b-2) + (b-3)) is within the above range, it is considered that the strong adsorption to the coloring material surface can be maintained for a long time, and the storage stability is further improved.

[0178] When the structural unit (b-3) is contained, the molar ratio of the structural unit (b-1) in the B segment to the total amount of the structural unit (b-2) and the structural unit (b-3) ((b-1) / {(b-2)+(b-3)}) is preferably 5 / 95 or more, more preferably 10 / 90 or more, further preferably 20 / 80 or more, preferably 95 / 5 or less, more preferably 80 / 20 or less, further preferably 60 / 40 or less. When the molar ratio ((b-1) / {(b-2)+(b-3)}) is within the above range, it is considered that the strong adsorption to the coloring material surface can be maintained for a long time, and the storage stability is further improved.

[0179] The B segment may contain other structural units in addition to the structural units (b-1), (b-2) and (b-3). Specific examples of vinyl monomers that can form other structural units of the B segment include the same monomers as those exemplified as specific examples of monomers that can form structural units of the A block.

[0180] When other structural units are contained, the content of the other structural units is preferably 90 mol% or less, more preferably 70 mol% or less, and further preferably 20 mol% or less, based on 100 mol% of the structural units constituting the B segment.

[0181] (Block Copolymer)

[0182] The structure of the block copolymer is preferably a linear block copolymer. In addition, the linear block copolymer may be of any structure (arrangement), but from the perspective of the physical properties of the linear block copolymer or the physical properties of the composition, when the A segment is represented by A and the B segment is represented by B, it is preferably selected from (AB) m Type, (AB) m -Type A, (BA) m -B type (m is an integer greater than 1, such as an integer of 1 to 3) of the copolymer of at least one structure. Among them, from the viewpoint of operability during processing and physical properties of the composition, AB type block copolymers are preferred. It is believed that by constituting an AB type block copolymer, the structural units of the A segment and the structural units (b-2) of the B segment are centralized, and can effectively interact with the coloring material, the dispersion medium, and the binder resin appropriately. The block copolymer may also have other blocks other than the A segment and the B segment. As the block copolymer, a diblock copolymer consisting of one A block and one B block, and a triblock copolymer consisting of one A block and two B blocks are preferred.

[0183] Among the total structural units constituting the block copolymer, the content of the total molar number of the structural units constituting the A segment is preferably 30 mol% or more, more preferably 35 mol% or more, further preferably 40 mol% or more, preferably 75 mol% or less, more preferably 70 mol% or less, further preferably 65 mol% or less, and particularly preferably 60 mol% or less.

[0184] Among the total structural units constituting the block copolymer, the content of the total molar number of the structural units constituting the B segment is preferably 25 mol% or more, more preferably 30 mol% or more, further preferably 35 mol% or more, particularly preferably 40 mol% or more, preferably 70 mol% or less, more preferably 65 mol% or less, further preferably 60 mol% or less.

[0185] In the block copolymer, the molar ratio of the total molar amount of the structural units constituting the A segment to the total molar amount of the structural units constituting the B segment (A segment / B segment) is preferably 30 / 70 or more, more preferably 35 / 65 or more, further preferably 40 / 60 or more, preferably 75 / 25 or less, more preferably 70 / 30 or less, further preferably 65 / 35 or less, and particularly preferably 60 / 40 or less. If the molar ratio (A segment / B segment) is 30 / 70 or more, the aggregation with the coloring material is prevented due to the steric repulsion of the A segment, and the storage stability is improved. If it is 75 / 25 or less, it is believed that the strong adsorption of the basic group to the surface of the coloring material can be maintained for a long time, and the storage stability is further improved.

[0186] The weight average molecular weight (Mw) of the block copolymer is preferably 5,000 or more, more preferably 8,000 or more, further preferably 10,000 or more, preferably 40,000 or less, more preferably 30,000 or less, and further preferably 20,000 or less. If the weight average molecular weight is within the above range, the dispersibility when used as a dispersant is better. The molecular weight of the block copolymer is measured by gel permeation chromatography (hereinafter referred to as "GPC").

[0187] The molecular weight distribution (Mw / Mn) of the block copolymer is preferably less than 3.0, more preferably less than 2.0, and further preferably less than 1.7. If the molecular weight distribution (Mw / Mn) is less than 3.0, the dispersibility when used as a dispersant is better. It should be noted that the molecular weight distribution is obtained by (weight average molecular weight (Mw) of the block copolymer) / (number average molecular weight (Mn) of the block copolymer). The smaller the value of the molecular weight distribution, the narrower the molecular weight distribution becomes, and when the value is 1.0, the molecular weight distribution has the narrowest amplitude. That is, the lower limit of the molecular weight distribution is 1.0.

[0188] From the viewpoint of the adsorption property to the coloring material and the dispersibility of the coloring material, the amine value of the block copolymer is preferably 10 mgKOH / g or more, more preferably 25 mgKOH / g or more, further preferably 40 mgKOH / g or more, and is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, further preferably 100 mgKOH / g or less.

[0189] When the block copolymer includes a structural unit having an acidic group, the acid value of the block copolymer is preferably 5 mgKOH / g or more, preferably 50 mgKOH / g or less. By setting the acid value within this range, the block copolymer can appropriately act with a binder resin (alkali-soluble resin) without damaging the affinity between the block copolymer and the coloring material.

[0190] (Method for preparing block copolymer)

[0191] The following methods can be cited as methods for preparing the block copolymer: a method of first preparing segment A through a polymerization reaction of a vinyl monomer, and then polymerizing a monomer of segment B on segment A; a method of first preparing segment B, and then polymerizing a monomer of segment A on segment B; a method of preparing segment A and segment B separately, and then coupling segment A and segment B; a method of first preparing segment A, and then polymerizing a monomer composition containing vinyl monomers capable of forming structural units (b-1) and structural units (b-2) on segment A, and mixing the structural units (b-1) and (b-2) in the obtained polymer; 2); a method for polymerizing a monomer composition containing a vinyl monomer capable of forming structural units (b-1) and structural units (b-2), polymerizing a monomer of a segment A on the polymer, and quaternizing a portion of the tertiary amine structure of the structural unit (b-2) in the obtained polymer; a method for separately preparing a segment A and a segment having structural units (b-1) and structural units (b-2), coupling these segments, and then quaternizing a portion of the tertiary amine structure of the structural unit (b-2) in the obtained polymer.

[0192] The polymerization method is not particularly limited, but the living polymerization method is preferred. That is, as the block copolymer, the block copolymer polymerized by the living polymerization method is preferred. Among the four elementary reactions of the initiation reaction, growth reaction, termination reaction, and chain transfer reaction in the chain polymerization, the living polymerization method is not easy to have a termination reaction and a chain transfer reaction. When the reaction point (polymerization growth end) is not deactivated, the vinyl monomer reacts and the polymer chain grows, so it is preferred from the perspective of easily preparing a polymer with a precisely controlled molecular weight distribution and a uniform composition. Among the living polymerization methods, there are living radical polymerization methods, living anion polymerization methods, living cationic polymerization methods, etc. Among them, from the viewpoint of the simplicity of polymerization, the living radical polymerization method is preferred. In addition, the living radical polymerization method is easy to prepare a polymer with a precisely controlled molecular weight distribution and a uniform composition while maintaining the simplicity and versatility of the free radical polymerization method (existing free radical polymerization method), which is also preferred from this point of view.

[0193] In the living radical polymerization method, there are the following methods, depending on the method of stabilizing the polymerization growth end: a method using a compound that can generate a nitroxide radical (nitroxide method: NMP method); a method using a metal complex such as copper or ruthenium and a halogenated compound as a polymerization initiator compound, and living polymerization from the polymerization initiator compound (ATRP method); a method using a dithiocarboxylate or xanthate compound (RAFT method); a method using an organic tellurium compound (TERP method); a method using an organic iodide (ITP method); a method using an iodine compound as a polymerization initiator compound and an organic compound such as a phosphorus compound, a nitrogen compound, an oxygen compound or a hydrocarbon as a catalyst (reversible chain transfer catalytic polymerization: RTCP method, reversible complex mediated polymerization: RCMP method), etc. Among these methods, the TERP method is preferably used from the viewpoints of the diversity of monomers that can be used, the molecular weight control in the high molecular weight region, the uniformity of the composition or the coloring.

[0194] The TERP method refers to a method of polymerizing a radical polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent, for example, methods described in International Publication Nos. 2004 / 14848, 2004 / 14962, 2004 / 072126, 2004 / 096870, and 2020 / 116144.

[0195] Specific examples of the TERP polymerization method include the following (a) to (d).

[0196] (a) A method of polymerizing a vinyl monomer using an organic tellurium compound represented by formula (6).

[0197] (b) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by formula (6) and an azo polymerization initiator.

[0198] (c) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the formula (6) and an organic ditelluride represented by the formula (7).

[0199] (d) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by formula (6), an azo polymerization initiator, and an organic ditelluride represented by formula (7).

[0200]

[0201] R 61 -Te-Te-R 61 (7)

[0202] [In formula (6), R 61represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms, R 62 and R 63 Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R 64 represents an alkyl group, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group having 1 to 8 carbon atoms. 61 represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms.]

[0203] As the organic tellurium compound represented by formula (6), specifically, ethyl-2-methyl-2-n-butyl tellurium-propionate, ethyl-2-n-butyl tellurium-propionate, (2-hydroxyethyl)-2-methyl-methyl tellurium-propionate, etc., and organic tellurium compounds described in International Publication No. 2004 / 14848, International Publication No. 2004 / 14962, International Publication No. 2004 / 072126, International Publication No. 2004 / 096870, and International Publication No. 2020 / 116144 can be cited. As specific examples of the organic ditelluride represented by formula (7), dimethyl ditelluride, dibutyl ditelluride, etc. can be cited. The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in conventional free radical polymerization. For example, 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis(1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2'-azobisisobutyrate (MAIB), 4,4'-azobis(4-cyanovaleric acid) (ACVA), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70), 2,2'-azobis(N-butyl-2-methylpropionamide) (VAm-110), etc. can be mentioned.

[0204] In the polymerization step, in a container replaced with an inert gas, an azo polymerization initiator and / or an organic ditellurium compound represented by formula (7) are further mixed with the vinyl monomer and the organic tellurium compound represented by formula (6) for the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution, etc., depending on the type of the vinyl monomer. At this time, nitrogen, argon, helium, etc. can be cited as the inert gas. Argon and nitrogen are preferred. The amount of the vinyl monomer in (a), (b), (c) and (d) can be appropriately adjusted according to the physical properties of the target copolymer.

[0205] The polymerization reaction can also be carried out without solvent, but it is also possible to use a non-protic solvent or a protic solvent commonly used in free radical polymerization and stir the mixture to carry out. As a non-protic solvent that can be used, for example, acetonitrile, methyl ethyl ketone, anisole, benzene, toluene, propylene glycol monomethyl ether acetate, ethyl acetate, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), acetone, dioxane, chloroform, carbon tetrachloride, etc. can be listed. In addition, as a protic solvent, for example, water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, diacetone alcohol, etc. can be listed. The solvent can be used alone or in combination of two or more. The amount of the solvent can be appropriately adjusted, for example, preferably 0.01ml to 50ml per gram of vinyl monomer. In the polymerization reaction, a surfactant and / or a dispersant may be further used in addition to the solvent.

[0206] The reaction time can be appropriately adjusted according to the molecular weight or molecular weight distribution of the copolymer obtained, but is usually 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 can also be pressurized or depressurized. In addition, the polymerization reaction can also be carried out by light irradiation. After the polymerization reaction is completed, the solvent used, the residual vinyl monomer, etc. can be removed from the reaction mixture obtained by conventional separation and purification means to separate the target copolymer.

[0207] The growing end of the copolymer obtained by polymerization is -TeR from the tellurium compound. 61 (Where R 61 The tellurium atoms are in the form of the copolymer (same as above), although they are continuously deactivated by the operation in the air after the polymerization reaction is completed, they sometimes still remain. Since copolymers with tellurium atoms remaining at the ends are colored or have poor thermal stability, it is preferred to remove the tellurium atoms. Methods for removing tellurium atoms include free radical reduction methods; adsorption methods using activated carbon, etc.; metal adsorption methods using ion exchange resins, etc., and these methods can also be used in combination. It should be noted that the other end of the copolymer obtained by the polymerization reaction (the end on the opposite side to the growing end) is -CR from the tellurium compound. 62 R 63 R 64 (Where R 62 , R 63 and R 64 With R in formula (6) 62 , R 63 and R 64 Therefore, the copolymer obtained by the TERP method does not have a substituent containing a sulfur atom at the terminal.

[0208] When the tertiary amine group of the structural unit having a basic group is quaternized, examples of the quaternizing agent include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, and methyl iodide; aryl halides such as benzyl chloride, benzyl bromide, and benzyl iodide; diaryl sulfates such as diphenyl sulfate; dialkyl sulfates such as dimethyl sulfate, diethyl sulfate, and di-n-propyl sulfate; aromatic alkyl sulfonates such as methyl p-toluenesulfonate and ethyl p-toluenesulfonate. Among them, aryl halides such as benzyl chloride, benzyl bromide, and benzyl iodide, dialkyl sulfates such as dimethyl sulfate, diethyl sulfate, and di-n-propyl sulfate, and aromatic alkyl sulfonates such as methyl p-toluenesulfonate and ethyl p-toluenesulfonate are preferred, and benzyl chloride, dimethyl sulfate, and methyl p-toluenesulfonate are more preferred. Alkyl groups and arylalkyl groups derived from the quaternizing agent are introduced into the structure after quaternization.

[0209] As a method for quaternizing a part of the tertiary amine structure of the structural unit having a basic group in the polymer, a method of contacting the polymer with a quaternizing agent can be cited. Specifically, a method of polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit having a basic group, adding a quaternizing agent to the reaction solution and stirring can be cited. The temperature of the reaction solution to which the quaternizing agent is added is preferably 55° C. to 65° C., and the stirring time is preferably 5 hours to 20 hours.

[0210] <Dispersant>

[0211] The dispersant of the present invention contains the block copolymer as a main component (more than 50% by mass). The block copolymer is adsorbed on the coloring material through the basic group (B segment) in its structure, and plays a role in improving the dispersibility of the coloring material. That is, the dispersant of the present invention is a component that makes the coloring material well dispersed by this effect, so there is no particular limitation on the type of the dispersed coloring material.

[0212] The dispersant of the present invention has high dispersibility of a coloring material and can be suitably used as a dispersant for a coloring composition for a color filter.

[0213] In addition, the dispersant of the present invention has high dispersibility of coloring materials, and therefore can also be used in spray inks, printing inks, writing instrument inks, coatings, etc. It should be noted that by appropriately changing the composition of the block copolymer, it can be used not only in coloring compositions using organic solvents, but also in coloring compositions using aqueous solvents.

[0214] The content of the block copolymer in the dispersant is 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more. The dispersant may be composed only of the block copolymer.

[0215] <Coloring Composition>

[0216] The coloring composition of the present invention contains the above-mentioned dispersant, a coloring material, and a dispersion medium. The coloring composition of the present invention has high dispersibility of the coloring material and can be suitably used as a coloring composition for color filters.

[0217] (Coloring material)

[0218] The type and particle size of the coloring material can be appropriately selected according to its use, and there is no particular limitation. The coloring composition preferably contains a pigment as a coloring material. As a pigment, it can be any one of an organic pigment and an inorganic pigment, but an organic pigment with an organic compound as the main component is particularly preferred. As a pigment, for example, red pigments, yellow pigments, orange pigments, blue pigments, green pigments, purple pigments and other pigments of various colors can be listed. The structure of the pigment can be listed as monoazo pigments, diazo pigments, condensed diazo pigments and other azo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindolinone pigments, quinacridone pigments, indigo pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, pyrenone pigments and other polycyclic pigments. The pigment contained in the coloring composition can be only one or more.

[0219] Specific examples of the pigment include CI 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 and the like; CI Pigment Yellow 1, 3, 5, 6, 14, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 93, 97, 98, 104, 108, 110, 138, 139, 147, 150, 151, 152 CI Pigment Orange 36, 38, 43 and other orange pigments; CI Pigment Blue 15, 15:2, 15:3, 15:4, 15:6, 16, 22, 60 and other blue pigments; CI Pigment Green 7, 36, 58, 59, 62, 63, aluminum phthalocyanine, polyhalogenated aluminum phthalocyanine, aluminum hydroxide phthalocyanine, diphenoxy phosphinyl oxyaluminum phthalocyanine, diphenyl phosphinyl oxyaluminum phthalocyanine, polyhalogenated diphenoxy phosphinyl oxyaluminum phthalocyanine, polyhalogenated diphenyl phosphinyl oxyaluminum phthalocyanine and other green pigments; CI Pigment Violet 23, 32, 50 and other purple pigments, etc. The pigments are preferably CI Pigment Red 177, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 291, CI Pigment Blue 15, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, Pigment Green 63, etc.

[0220] In addition, the coloring material may also contain a pigment derivative as a dispersing aid. In order to ionically bond with the basic group in the block copolymer contained in the dispersant and adsorb it, as the pigment derivative, it is preferred to contain an acidic pigment derivative with an acidic group. The pigment derivative is a substance in which an acidic group is introduced into the pigment skeleton. As a pigment skeleton, it is preferred to have a skeleton identical or similar to the coloring material constituting the coloring composition, and a skeleton identical or similar to the compound as the raw material of the coloring material. As specific examples of the pigment skeleton, azo pigment skeletons, phthalocyanine pigment skeletons, anthraquinone pigment skeletons, triazine pigment skeletons, acridine pigment skeletons, perylene pigment skeletons, etc. can be cited. As the acidic group introduced in the pigment skeleton, carboxyl, phosphoric acid, and sulfonic acid groups are preferred. It is explained that from the perspective of the convenience of synthesis and the strength of the acidity, sulfonic acid groups are preferred. In addition, the acidic group can be directly bonded to the pigment skeleton, but it can also be bonded to the pigment skeleton via hydrocarbon groups such as alkyl or aryl groups, esters, ethers, sulfonamides, and aminoester bonds.

[0221] The amount of the pigment derivative used is not particularly limited, but is preferably 4 to 17 parts by mass based on 100 parts by mass of the coloring material, for example.

[0222] From the viewpoint of brightness, the upper limit of the content of the coloring material in the coloring composition is usually 80% by mass, preferably 70% by mass, and more preferably 60% by mass in the total solid content of the coloring composition. In addition, the lower limit of the content of the coloring material in the coloring composition is usually 10% by mass, preferably 20% by mass, and more preferably 30% by mass in the total solid content of the coloring composition. Here, the solid content refers to the components other than the dispersion medium described later.

[0223] The content of the dispersant in the coloring composition is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and further preferably 10 to 80 parts by mass, relative to 100 parts by mass of the coloring material. When the content of the dispersant is within the above range, the viscosity of the coloring composition is good.

[0224] (Dispersion Medium)

[0225] As the dispersion medium used in the present invention, any dispersion medium can be appropriately selected and used as long as it disperses or dissolves other components constituting the coloring composition, does not react with these components, and has moderate volatility. For example, conventionally known organic solvents can be used, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monon-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monon-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether and the like glycol monoalkyl ethers; ethylene glycol dimethyl ether, ethylene glycol Diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether and other glycol dialkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, di Propylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate and other glycol diacetates; ethylene glycol diacetates, 1,3-butanediol diacetate, 1,6-hexanol diacetate and other glycol diacetates; cyclohexanol acetate and other alkyl acetates; amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether and other ethers; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone Ketones such as methyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl amyl ketone; monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, methoxymethyl amyl alcohol, glycerol, benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, dicyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, cumene;Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone and other chain or cyclic esters; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethyl pentanone; nitriles such as acetonitrile and benzonitrile, etc. From the viewpoints of dispersibility of coloring materials, solubility of dispersants, coating properties of coloring compositions, etc., the organic solvent is preferably glycol alkyl ether acetate, glycol monoalkyl ether, monohydric or polyhydric alcohol. The dispersion medium contained in the coloring composition may be only one or more. ;

[0226] When the pixels of the color filter are formed by photolithography, the boiling point of the dispersion medium is preferably 100°C to 200°C (under a pressure of 1013.25 hPa. The boiling point below is all under this condition), and more preferably 120°C to 170°C. Among the above-mentioned dispersion media, glycol alkyl ether acetates are preferred from the perspective of good balance of coating properties, surface tension, etc. and relatively high solubility of the constituent components in the coloring composition. Glycol alkyl ether acetates can be used alone or in combination with other dispersion media. In addition, it is also preferred to use a dispersion medium with a boiling point of 150°C or above. By using a dispersion medium with a high boiling point, the destruction of the relationship between the coloring compositions caused by rapid drying of the coloring composition can be suppressed. It should be noted that the dispersion medium with a boiling point of 150°C or above may also be glycol alkyl ether acetates.

[0227] The content of the dispersion medium in the coloring composition is not particularly limited and can be appropriately adjusted. The upper limit of the dispersion medium content in the coloring composition is generally 99% by mass. In addition, considering the viscosity suitable for coating the coloring composition, the lower limit of the dispersion medium content in the coloring composition is generally 70% by mass, preferably 80% by mass. The above-mentioned dispersion medium can be used as a solvent for dissolving and removing the formed precipitate from the coloring composition.

[0228] (Binder resin)

[0229] The coloring composition may contain a binder resin (the binder resin does not include the above-mentioned block copolymer). As the binder resin, alkali-soluble resins, polymerizable compounds (polymerizable resins, monomers having one polymerizable unsaturated bond in the molecule, monomers having two or more polymerizable unsaturated bonds in the molecule, oligomers, etc.), thermosetting resins, thermoplastic resins, etc. can be listed. These can be used alone or in combination of two or more. Among them, alkali-soluble resins and / or polymerizable compounds are preferred.

[0230] The content of the binder resin in the colored composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, based on the total amount of the binder resin used in the total solid content of the colored composition.

[0231] (Alkali soluble resin)

[0232] The alkali-soluble resin is not particularly limited as long as it acts as a binder for the coloring material and is soluble in a developer (preferably an alkali developer) used in the development process when preparing the color filter, but a resin having an acidic group such as a carboxyl group or a phenolic hydroxyl group is preferred.

[0233] Examples of the alkali-soluble resin include: a resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy groups of a copolymer of an epoxy-containing (meth)acrylate and other free radical polymerizable monomers, or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction; a straight-chain resin containing a carboxyl group in the main chain; a resin obtained by adding an epoxy-containing unsaturated compound to the carboxyl part of a carboxyl-containing resin; a (meth)acrylic resin; an epoxy (meth)acrylate resin having a carboxyl group, etc. These can be used alone or in combination of two or more.

[0234] The alkali-soluble resin is preferably a random copolymer containing a structural unit derived from a carboxyl-containing vinyl monomer, a structural unit derived from a (meth)acrylate, and styrene; a synthetic resin in which a (meth)acrylate group is introduced into an epoxy resin; or a random copolymer containing a structural unit derived from a carboxyl-containing vinyl monomer and a structural unit derived from a (meth)acrylate. The carboxyl-containing vinyl monomer is preferably (meth)acrylic acid. Examples of the (meth)acrylate include 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, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, glyceryl mono(meth)acrylate, glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

[0235] The total content of the structural unit derived from the carboxyl group-containing vinyl monomer and the structural unit derived from the (meth)acrylate in the alkali-soluble resin is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. In addition, the content of the structure derived from the carboxyl group-containing vinyl monomer in the alkali-soluble resin is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and preferably 90% by mass or less, and more preferably 70% by mass or less.

[0236] Among the alkali-soluble resins, random copolymers of carboxyl-containing vinyl monomers and (meth) acrylic acid esters are preferred. As specific examples of such copolymers, random copolymers of (meth) acrylic acid and butyl (meth) acrylic acid, random copolymers of (meth) acrylic acid and benzyl (meth) acrylic acid, random copolymers of (meth) acrylic acid and butyl (meth) acrylic acid and benzyl (meth) acrylic acid, etc. can be cited. From the viewpoint of the affinity of the alkali-soluble resin and the coloring material, the alkali-soluble resin is particularly preferably a random copolymer of (meth) acrylic acid and benzyl (meth) acrylic acid. In the copolymer of carboxyl-containing vinyl monomers and (meth) acrylic acid esters, the content of (meth) acrylic acid is generally 5% to 90% by mass, preferably 10% to 70% by mass, and more preferably 20% to 70% by mass in the total monomer components. The polymerization method of these random copolymers is not particularly limited, but from the viewpoint of alkali solubility, active radical polymerization is preferred.

[0237] The alkali-soluble resin may also be a resin having a carbon-carbon double bond capable of free radical polymerization in the side chain. By having a double bond in the side chain, the photocurability of the coloring composition of the present invention is improved, thereby further improving the resolution and adhesion. As a method for introducing a carbon-carbon double bond capable of free radical polymerization in the side chain, for example, a method of reacting compounds such as (meth) glycidyl acrylate, (meth) (3,4-epoxycyclohexyl) methyl acrylate, ortho (or meta, or para) vinyl benzyl glycidyl ether with the acidic group of the binder resin can be cited.

[0238] The Mw of the alkali-soluble resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 20,000. When the Mw of the alkali-soluble resin is 3,000 or more, the heat resistance and film strength of the colored layer formed from the colored composition are good, and when the Mw is 100,000 or less, the alkali developability of the coated film is better.

[0239] The acid value of the alkali-soluble resin is preferably 20 mgKOH / g to 170 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and further preferably 90 mgKOH / g to 150 mgKOH / g. If the acid value of the alkali-soluble resin is 20 mgKOH / g or more, the alkali developability when the coloring composition is a coloring layer is better, and if it is 170 mgKOH / g or less, the heat resistance is good.

[0240] The alkali-soluble resin contained in the coloring composition may be only one or more. In the coloring composition, the content of the alkali-soluble resin is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and further preferably 20 to 80 parts by mass, relative to 100 parts by mass of the coloring material.

[0241] (Polymerizable compound)

[0242] Examples of the polymerizable compound include polymerizable resins (e.g., resins having crosslinking groups such as (meth) acrylic acid compounds and cinnamic acid introduced into linear polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups via isocyanate groups, aldehyde groups, epoxy groups, and the like), compounds having one polymerizable unsaturated bond in the molecule (e.g., monofunctional (meth) acrylic acid monomers ((meth) acrylic acid alkyl esters, (meth) acrylic acid arylalkyl esters, etc.)), compounds having two or more polymerizable unsaturated bonds in the molecule (e.g., multifunctional (meth) acrylic acid monomers (di(meth) acrylic acid esters of diols, poly(meth) acrylic acid esters of trivalent or higher polyols, etc.)). Examples of polymerizable unsaturated bonds include carbon-carbon double bonds and carbon-carbon triple bonds. These can be used alone or in combination of two or more. Among them, compounds having two or more polymerizable unsaturated bonds in the molecule are preferred.

[0243] Examples of the monomer having two or more polymerizable unsaturated bonds in the molecule of the polymerizable compound include bisphenol A di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0244] The content of the polymerizable compound in the coloring composition is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, relative to 100 parts by mass of the coloring material. If the content of the polymerizable compound is within the above range, sufficient curability can be obtained and alkali developability is also good. It is also preferred to use an alkali-soluble resin and a polymerizable compound together as a binder resin.

[0245] (Thermosetting resin, thermoplastic resin)

[0246] Examples of the thermosetting resin or thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, phenol resin, polyester resin, (meth)acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, cellulose, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin, and the like.

[0247] (Photopolymerization Initiator)

[0248] The coloring composition of the present invention may contain a photopolymerization initiator as required. This can impart radiation sensitivity to the coloring composition. The photopolymerization initiator is a compound that can generate an active substance that initiates polymerization of a polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far infrared light, electron beams, and X-rays.

[0249] Examples of the photopolymerization initiator include thioxanthone compounds, acetophenone compounds, bisimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, and imide sulfonate compounds. The photopolymerization initiator may be used alone or in combination of two or more.

[0250] In the coloring composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, relative to 100 parts by mass of the polymerizable compound. In this case, if the content of the photopolymerization initiator is too small, exposure curing may be insufficient, while if the content is too large, the formed coloring layer may easily fall off from the substrate during development.

[0251] (Other ingredients)

[0252] In addition to the above-mentioned additives, other additives may be added to the coloring composition of the present invention within the range that does not impair the preferred physical properties of the present invention. As other additives, dispersants other than the above-mentioned block copolymers (urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, etc.), sensitizing pigments, thermal polymerization inhibitors, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants), plasticizers, organic carboxylic acid compounds, organic carboxylic anhydrides, antioxidants, ultraviolet absorbers, light stabilizers, pH adjusters, preservatives, mildew inhibitors, anti-aggregating agents, adhesion improvers, development improvers, storage stabilizers, etc. can be listed.

[0253] Examples of the sensitizing dye include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone, 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)benzo[6,7]benzoxazole, 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 and the like.

[0254] Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-tert-butyl-p-cresol, and β-naphthol.

[0255] Examples of the nonionic surfactant include fluorine-based surfactants (1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9,9,10,10-decyl) sulfonate, fluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc.), siloxane-type surfactants, polyoxyethylene-type surfactants (polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerol fatty acid esters, polyoxyethylene glycerol 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, polyoxyethylene sorbitan fatty acid esters, etc.), etc.

[0256] Examples of the anionic surfactant include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, higher alcohol sulfate ester salts, fatty alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, and special polymer surfactants.

[0257] Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.

[0258] Examples of the amphoteric surfactant include betaine compounds, imidazolium salts, imidazolines, and amino acids.

[0259] Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dioctanoate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and glyceryl triacetate.

[0260] Examples of the organic carboxylic acid compound 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, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid; aliphatic tricarboxylic acids such as trisaccharic acid and aconitic acid; aromatic carboxylic acids having a carboxyl group directly bonded to a phenyl group such as benzoic acid, phthalic acid, trimesic acid, pyromellitic acid, and tetraphenylene carboxylic acid; aromatic carboxylic acids having a carboxyl group bonded to a phenyl group via a carbon bond such as phenylacetic acid, 2-phenylpropionic acid, 3-phenylpropionic acid, phenylsuccinic acid, and 5-phenyl-2,4-pentadienoic acid, etc. By containing the organic carboxylic acid compound, alkali developability and substrate staining can be improved.

[0261] Examples of the organic carboxylic anhydride include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalene dicarboxylic anhydride, etc. By containing the organic carboxylic anhydride, alkali developability and substrate staining can be improved.

[0262] <Method for preparing coloring composition>

[0263] The coloring composition can be prepared by mixing a coloring material, a dispersant (or a dispersant solution), a dispersion medium, an adhesive resin added as needed, a photopolymerization initiator, and other additives. Mixing can be performed using a mixing and dispersing machine such as a paint stirrer, a bead mill, a ball mill, a dissolver, a kneader, etc. The coloring composition is preferably filtered after mixing. In the case where the coloring composition has alkali developability, it can be suitable for use in color filters. As an alkali developer, an aqueous solution containing an organic solvent or a surfactant and an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, etc. can be used.

[0264] <Color filter>

[0265] The color filter of the present invention includes a colored layer formed using the above-mentioned colored composition.

[0266] As a method for preparing a color filter, for example, the following method can be cited. First, on a transparent substrate such as a polyester resin, a polyolefin resin, a polycarbonate resin, a polymethyl methacrylate resin, etc., a thermosetting resin sheet such as an epoxy resin, an unsaturated polyester resin, a poly (meth) acrylic resin, etc., and various glasses, for example, a coloring composition dispersed with a red pigment is applied, and then a soft bake (pre-bake) is performed to evaporate the solvent (dispersion medium) to form a coating film. Then, after the coating film is exposed via a photomask, an alkaline developer (containing an organic solvent or a surfactant and an aqueous solution of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, etc.) is used to develop and dissolve and remove the unexposed portion of the coating film. Then, a pixel array having a red pixel pattern arranged in a prescribed arrangement is formed by hard baking (post-bake). Next, a green coloring composition or a blue coloring composition is used, and each coloring composition is applied, soft baked, exposed, developed and hard baked in the same manner as above, and a green pixel array and a blue pixel array are sequentially formed on the same substrate. Thus, a color filter having a pixel array of the three primary colors of red, green and blue is obtained on the substrate. However, the order of forming the pixels of each color in the present invention is not limited to the above order. In addition, a black matrix can also be provided on the transparent substrate for forming the pixel array of the three primary colors of red, green and blue.

[0267] When the coloring composition is applied to the substrate, an appropriate coating method such as spray coating, roll coating, spin coating, slot die coating, or bar coating can be used, and spin coating and slot die coating are particularly preferably used.

[0268] After forming a protective film on the pixel pattern obtained as required, a transparent conductive film (ITO, etc.) is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to form a color filter.

[0269] The color filter of the present invention has high brightness, dimensional accuracy, etc., and can be suitably used in color liquid crystal display elements, color camera tube elements, color sensors, organic EL display elements, electronic paper, and the like.

[0270] Example

[0271] The present invention is further described in detail below based on specific examples. The present invention is not limited to the following examples and can be implemented with appropriate changes without changing its purpose. It should be noted that the polymerization rate, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), amine value and acid value of the block copolymer and the viscosity of the coloring composition are evaluated according to the following method.

[0272] The abbreviations have the following meanings: BTEE: ethyl-2-methyl-2-n-butyltelluryl-propionate, DBDT: dibutyl ditelluride, AIBN: 2,2'-azobis(isobutyronitrile), CL5MA: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate, CL5A: 5 mol caprolactone adduct of 2-hydroxyethyl acrylate, H2EGM: terminal hydroxyl polyethylene glycol (degree of polymerization = 2) monomethacrylate, M4EGM: polyethylene glycol (degree of polymerization = 4) methyl ether methacrylate, M9EGM: polyethylene glycol (degree of polymerization = 5) monomethacrylate. 9) Methyl ether methacrylate, HEMA: 2-hydroxyethyl methacrylate, HEA: 2-hydroxyethyl acrylate, BMA: n-butyl methacrylate, BA: n-butyl acrylate, CHMA: cyclohexyl methacrylate, BzMA: benzyl methacrylate, DMAEMA: dimethylaminoethyl methacrylate, DMAEA: dimethylaminoethyl acrylate, DMAEMA·BzCl: methacryloyloxyethylbenzyldimethylammonium chloride, MAA: methacrylic acid, BzCl: benzyl chloride, PMA: propylene glycol monomethyl ether acetate.

[0273] (Polymerization rate)

[0274] The results were measured using a nuclear magnetic resonance (NMR) measuring device (manufactured by Bruker BioSpin, model: AVANCE500 (frequency 500 MHz)). 1 H-NMR (solvent: CDCl3, internal standard: tetramethylsilane) The integration ratio of the peak derived from the monomer and the peak derived from the polymer was determined from the obtained NMR spectrum to calculate the polymerization rate of the monomer.

[0275] (Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn))

[0276] It was obtained by gel permeation chromatography (GPC) using a high performance liquid chromatograph (manufactured by Tosoh Corporation, model HLC-8320). The chromatographic column used was a SHODEX KF-603 (Φ6.0 mm×150 mm) (manufactured by SHODEX Corporation), the mobile phase was a lithium bromide (10 mmol / L)-acetic acid (10 mmol / L)-methylpyrrolidone solution, and the detector was a differential refractometer. The measurement conditions were as follows: column temperature 40°C, sample concentration 10 mg / mL, sample injection volume 10 μL, flow rate 0.2 mL / min. Polystyrene (molecular weight 70,500, 37,900, 19,920, 10,200, 4,290, 2,630, 1,150) was used as a standard substance to prepare a standard curve (calibration curve), and the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured. The molecular weight distribution (Mw / Mn) was calculated from the measured values.

[0277] (Amine value)

[0278] The amine value represents the mass of potassium hydroxide (KOH) equivalent to the alkaline component per gram of solid content. The sample to be measured is dissolved in tetrahydrofuran, and the resulting solution is neutralized and titrated with a hydrochloric acid (0.1 mol / L)-propanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). The inflection point of the titration pH curve is taken as the titration endpoint, and the amine value (B) is calculated according to the following formula.

[0279] B=56.11×Vs×0.1×f / w

[0280] B: amine value (mgKOH / g), Vs: amount of hydrochloric acid (0.1 mol / L)-propanol solution required for titration (mL), f: titer of hydrochloric acid (0.1 mol / L)-propanol solution, w: mass of the sample to be measured (g) (solid content conversion value) (acid value)

[0281] The acid value is a value indicating the mass of potassium hydroxide (KOH) required to neutralize the acidic components per gram of solid content. The sample to be measured is dissolved in tetrahydrofuran, and a few drops of 1.0 w / v% phenolphthalein ethanol (90) solution are added to the resulting solution as an indicator, and neutralization titration is performed using potassium hydroxide (0.1 mol / L)-ethanol solution. The moment when a small amount of red remains is regarded as the titration endpoint, and the acid value is calculated by the following formula.

[0282] A=56.11×Vs×0.1×f / w

[0283] A: Acid value (mgKOH / g), Vs: Amount of potassium hydroxide (0.1 mol / L)-ethanol solution required for titration (mL), f: Titer of potassium hydroxide (0.1 mol / L)-ethanol solution, w: Mass of sample to be measured (g) (converted to solid content)

[0284] (Initial viscosity, viscosity over time)

[0285] The viscosity (mPa·s) was measured using an E-type viscometer (trade name: RE-80L, manufactured by Toki Sangyo) at 25° C. and a rotor rotation speed of 60 rpm using a conical rotor (0.8°×R24).

[0286] The coloring composition was prepared and stored at 40° C. for 1 day, and then the initial viscosity was measured. Also, the coloring composition was prepared and stored at 40° C. for 1 week, and then the viscosity over time was measured.

[0287] (KOH (potassium hydroxide) solubility)

[0288] On a cleaned glass plate (50 mm × 50 mm), a coating film of the coloring composition was formed using a spin coater (trade name: MS-A100, manufactured by MIKASA) at 10000 rpm for 10 seconds, and dried at 100° C. for 5 minutes. Next, the glass plate with the coating film formed was immersed in a 0.1% potassium hydroxide aqueous solution, and the solubility was observed at 23° C. The solubility was evaluated according to the following criteria.

[0289] 0: After 1 hour, the pigment dispersion was almost completely peeled off from the glass substrate.

[0290] ×: After 1 hour, almost all of the pigment dispersion remained on the glass substrate.

[0291] <Synthesis of Block Copolymer>

[0292] (Block copolymer No. 1)

[0293] In a flask equipped with an argon inlet and a stirrer, 47.56 g of BMA, 129.40 g of CL5MA, 0.849 g of AIBN, and 75.85 g of PMA were placed, and after argon substitution, 7.78 g of BTEE and 4.50 g of DBDT were added, and the reaction was carried out at 60° C. for 22.5 hours to polymerize the A block. The polymerization rate was 99.0%.

[0294] A mixed solution of 59.95 g of DMAEMA, 13.28 g of HEMA, 0.424 g of AIBN, and 31.40 g of PMA, which had been purged with argon in advance, was added to the reaction solution, and the mixture was reacted at 60° C. for 23.0 hours to polymerize the B block. The polymerization rate was 99.5%.

[0295] After the reaction was completed, the reaction solution was injected into the stirred n-heptane. The precipitated polymer was filtered and dried to obtain block copolymer No. 1. The obtained block copolymer No. 1 had an Mw of 19,235, an Mw / Mn of 1.64, and an amine value of 85 mgKOH / g.

[0296] (Block copolymer No. 2 to 16)

[0297] Block copolymers No. 2 to 12 were prepared in the same manner as the preparation method of block copolymer No. 1. Tables 2 and 3 show the monomers used, organic tellurium compounds (BTEE), organic ditellurium compounds (DBDT), azo polymerization initiators (AIBN), solvents (PMA), reaction temperatures, reaction times, and polymerization rates. In addition, Tables 4 and 5 show the composition, Mw, Mw / Mn, amine value, and acid value of each block copolymer. It should be noted that the content of each structural unit in the copolymer is calculated from the addition ratio of the monomers used in the polymerization reaction and the polymerization rate.

[0298] (Block copolymer No.17)

[0299] 392 mg of BzCl was added to 7.81 g of a PMA solution containing 5.0 g of the solid content of block copolymer No. 1, and the mixture was reacted at 60° C. for 6 hours for quaternization, and diluted with PMA to obtain a solution of block copolymer No. 17. The obtained block copolymer No. 17 had an Mw of 13,089, an Mw / Mn of 1.22, and an amine value of 46 mgKOH / g.

[0300] Table 2

[0301]

[0302] Table 3

[0303]

[0304] <Synthesis of Alkali-Soluble Resin (Binder Resin)>

[0305] A flask equipped with an argon inlet and a stirrer was charged with 20.0 g of MAA, 80.0 g of BzMA, and 290.0 g of PMA. After argon substitution, 1.5 g of AIBN, 2.0 g of n-dodecyl mercaptan, and 10.0 g of PMA were added and the temperature was raised to 90° C. While the solution was kept at 90° C., 40.0 g of MAA, 160.0 g of BzMA, 3.0 g of AIBN, 4.0 g of n-dodecyl mercaptan, and 25.0 g of PMA were added dropwise to the solution over 1.5 hours. 60 minutes after the addition was completed, the temperature was raised to 110° C., 0.3 g of AIBN and 5.0 g of PMA were added and reacted for 1 hour, and then 0.3 g of AIBN and 5.0 g of PMA were added and reacted for 1 hour, and then 0.3 g of AIBN and 5.0 g of PMA were added and reacted for 1 hour, and then 0.3 g of AIBN and 5.0 g of PMA were added and reacted for 1 hour.

[0306] The obtained reaction solution was cooled to room temperature, and 120.0 g of PMA was added to obtain a solution of an alkali-soluble resin having a nonvolatile content of 39.9%. The alkali-soluble resin had a Mw of 11,873, a Mw / Mn of 1.77, and an acid value of 127 mgKOH / g.

[0307] <Preparation of Coloring Composition>

[0308] (Coloring Composition No. 1)

[0309] 1.8 g of a pigment (CI Pigment Red 254), a solution of block copolymer No. 1 as a dispersant (40 parts by mass of the block copolymer relative to 100 parts by mass of the pigment), a solution of an alkali-soluble resin (40 parts by mass of the alkali-soluble resin relative to 100 parts by mass of the pigment), and PMA were added to a bead mill (trade name: DISPERMATCA, manufactured by VMA-GETZMANN GmbH) so that the pigment concentration became 10% by mass, and zirconium oxide beads were added. 50 g was added and stirred for 2 hours. After the stirring was completed, the beads were filtered off to prepare a coloring composition No. 1. The dispersion performance of the obtained coloring composition was evaluated, and the results are shown in Table 4. In addition, the evaluation result of KOH solubility of the coating film formed using the coloring composition No. 1 was "0".

[0310] (Coloring Composition No. 2 to 17)

[0311] Coloring compositions No. 2 to 17 were prepared in the same manner as the preparation method of coloring composition No. 1 except that the dispersant (block copolymer) was changed. The obtained coloring compositions were evaluated, and the results are shown in Tables 4 and 5. The evaluation result of KOH solubility of the coating film formed using coloring composition No. 15 was "x".

[0312] Table 4

[0313]

[0314] Table 5

[0315]

[0316] The A segments of block copolymers No. 1 to 11 and 17 substantially do not contain a structural unit (b-2) having a basic group, and the B segments contain a structural unit (b-1) having a hydroxyl group and a structural unit (b-2) having a basic group, and the molar ratio ((b-1) / (b-2)) of the structural unit (b-1) to the structural unit (b-2) in the B segments is 5 / 95 to 95 / 5.

[0317] Coloring compositions Nos. 1 to 12 using these block copolymers Nos. 1 to 11 and 17 as dispersants all had low initial viscosity and small difference in viscosity over time, and thus had high dispersibility of the coloring material.

[0318] The molar ratio ((b-1) / (b-2)) of the structural unit (b-1) to the structural unit (b-2) in the B segment of block copolymers Nos. 12 to 14 was less than 5 / 95. Coloring compositions Nos. 13 to 15 using these block copolymers Nos. 12 to 14 had low initial viscosity but high viscosity over time and poor storage stability.

[0319] Block copolymers Nos. 15 and 16 are cases where the B segment does not contain the structural unit (b-2) having a basic group. Coloring compositions Nos. 16 and 17 using these block copolymers Nos. 15 and 16 have high initial viscosities and poor dispersibility of the coloring material.

[0320] The present invention includes the following embodiments.

[0321] (Implementation 1) A block copolymer comprising an A segment and a B segment, characterized in that the A segment substantially does not contain a structural unit (b-2) having a basic group, the B segment contains a structural unit (b-1) having a hydroxyl group and a structural unit (b-2) having a basic group, and the molar ratio ((b-1) / (b-2)) of the structural unit (b-1) to the structural unit (b-2) in the B segment is 5 / 95 to 95 / 5.

[0322] (Embodiment 2) The block copolymer according to Embodiment 1, wherein the hydrogen bonding force component (δ h1 ) and the hydrogen bonding force component (δ h2 ) h1 -δ h2 ) is 0.5J 1 / 2 cm 1 / 2 ·mol -1 above.

[0323] (Embodiment 3) The block copolymer according to Embodiment 1 or 2, wherein the amine value of the block copolymer is 10 mgKOH / g to 150 mgKOH / g.

[0324] (Embodiment 4) The block copolymer according to any one of Embodiments 1 to 3, wherein the structural unit (b-1) is a structural unit represented by formula (1).

[0325]

[0326] [In formula (1), R 11 A represents a hydrogen atom or a methyl group. 11 represents an ester group, an amide group or a single bond, R 12 Represents a divalent hydrocarbon group, -R 13 -(OCO-R 14 ) m -base or -R 15 -(OR 16 ) n -Base, R 13 ~R 16Each independently represents a divalent hydrocarbon group, m represents an integer of 1 to 10, and n represents an integer of 1 to 10.]

[0327] (Embodiment 5) The block copolymer according to any one of Embodiments 1 to 4, wherein the structural unit (b-2) is a structural unit represented by formula (2).

[0328]

[0329] [In formula (2), R 21 A represents a hydrogen atom or a methyl group. 21 represents an ester group, an amide group or a single bond, R 22 Represents a divalent hydrocarbon group, R 23 and R 24 Each independently represents a hydrocarbon group which may contain a heteroatom, R 23 and R 24 Can bond with each other to form a ring structure.]

[0330] (Embodiment 6) The block copolymer according to any one of Embodiments 1 to 5, wherein the content of the structural unit derived from the (meth)acrylic acid group monomer in 100 mol % of the structural units constituting the A segment is 80 mol % or more.

[0331] (Embodiment 7) A block copolymer according to any one of Embodiments 1 to 6, wherein the A segment contains a structural unit derived from a (meth)acrylic monomer, and the (meth)acrylic monomer is one or more selected from the following monomers: a (meth)acrylic monomer having a chain alkyl group, a (meth)acrylic monomer having a cyclic alkyl group, a (meth)acrylic monomer having an aromatic group, a (meth)acrylic monomer having a hydroxyl group, a (meth)acrylic monomer having an alkoxy group, a (meth)acrylic monomer having an oxygen-containing heterocyclic group, a (meth)acrylic monomer having an amide group, and a (meth)acrylic monomer having an acidic group.

[0332] (Embodiment 8) The block copolymer according to any one of Embodiments 1 to 7, wherein the content of the structural unit (b-1) in 100 mol % of the structural units constituting the B segment is 5 mol % to 90 mol %.

[0333] (Embodiment 9) The block copolymer according to any one of Embodiments 1 to 8, wherein the molar ratio of the total molar amount of the structural units constituting the A segment to the total molar amount of the structural units constituting the B segment (A segment / B segment) is 30 / 70 to 75 / 25.

[0334] (Embodiment 10) The block copolymer according to any one of Embodiments 1 to 9, wherein the weight average molecular weight of the block copolymer is 5,000 to 40,000.

[0335] (Embodiment 11) The block copolymer according to any one of Embodiments 1 to 10, wherein the block copolymer is obtained by living polymerization and has a molecular weight distribution (Mw / Mn) of less than 3.0.

[0336] (Embodiment 12) A dispersant characterized by containing the block copolymer according to any one of Embodiments 1 to 11.

[0337] (Embodiment 13) A coloring composition characterized by containing a coloring material, a dispersion medium and the dispersant described in Embodiment 12.

[0338] (Embodiment 14) The colored composition according to Embodiment 13, which is used for a color filter.

[0339] (Embodiment 15) A color filter comprising a colored layer formed using the colored composition described in Embodiment 14.

Claims

1. A block copolymer having an A segment and a B segment, characterized in that: The A segment substantially does not contain a structural unit (b-2) having a basic group, The B segment contains a structural unit (b-1) having a hydroxyl group and a structural unit (b-2) having a basic group, The molar ratio of the structural unit (b-1) to the structural unit (b-2) in the B segment ((b-1) / (b-2)) is 5 / 95 to 95 / 5.

2. The block copolymer according to claim 1, wherein The hydrogen bonding force component (δ h1 ) and the hydrogen bonding force component (δ h2 ) h1 -δ h2 ) is 0.5J 1 / 2 cm 1 / 2 ·mol -1 above.

3. The block copolymer according to claim 1 or 2, wherein The amine value of the block copolymer is 10 mgKOH / g to 150 mgKOH / g.

4. The block copolymer according to claim 1 or 2, wherein The structural unit (b-1) is a structural unit represented by formula (1), In formula (1), R 11 A represents a hydrogen atom or a methyl group. 11 represents an ester group, an amide group or a single bond, R 12 Represents a divalent hydrocarbon group, -R 13 -(OCO-R 14 ) m -base or -R 15 -(OR 16 ) n -Base, R 13 ~R 16 Each independently represents a divalent hydrocarbon group, m represents an integer of 1 to 10, and n represents an integer of 1 to 10.

5. The block copolymer according to claim 1 or 2, wherein The structural unit (b-2) is a structural unit represented by formula (2), In formula (2), R 21 A represents a hydrogen atom or a methyl group. 21 represents an ester group, an amide group or a single bond, R 22 Represents a divalent hydrocarbon group, R 23 and R 24 Each independently represents a hydrocarbon group which may contain a heteroatom, R 23 and R 24 They can bond to each other to form a ring structure.

6. The block copolymer according to claim 1 or 2, wherein The content of the structural unit derived from the (meth)acrylic acid group monomer in 100 mol % of the structural units constituting the A segment is 80 mol % or more.

7. The block copolymer according to claim 1 or 2, wherein The A segment contains a structural unit derived from a (meth)acrylic acid-based monomer, and the (meth)acrylic acid-based monomer is one or more selected from the following monomers: a (meth)acrylic acid-based monomer having a chain alkyl group, a (meth)acrylic acid-based monomer having a cyclic alkyl group, a (meth)acrylic acid-based monomer having an aromatic group, a (meth)acrylic acid-based monomer having a hydroxyl group, a (meth)acrylic acid-based monomer having an alkoxy group, a (meth)acrylic acid-based monomer having an oxygen-containing heterocyclic group, a (meth)acrylic acid-based monomer having an amide group, and a (meth)acrylic acid-based monomer having an acidic group.

8. The block copolymer according to claim 1 or 2, wherein The content of the structural unit (b-1) in 100 mol % of the structural units constituting the B segment is 5 mol % to 90 mol %.

9. The block copolymer according to claim 1 or 2, wherein The molar ratio of the total molar amount of the structural units constituting the A segment to the total molar amount of the structural units constituting the B segment (A segment / B segment) is 30 / 70 to 75 / 25.

10. 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.

11. The block copolymer according to claim 1 or 2, wherein The block copolymer is obtained by living polymerization and has a molecular weight distribution (Mw / Mn) of less than 3.

0.

12. A dispersant, characterized in that: Containing the block copolymer according to claim 1 or 2.

13. A coloring composition, characterized in that Contains a coloring material, a dispersion medium and the dispersant according to claim 12. The colored composition according to claim 13 , which is used for a color filter.

15. A color filter, characterized in that: A colored layer is provided which is formed using the colored composition according to claim 14.

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