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 chain hydrocarbon group and a structural unit (b-2) having a basic group, the molar volume ratio ((b-1) / (b-2)) of the constituent unit (b-1) to the constituent unit (b-2) is 0.10-1.10, and the molar ratio ((b-1) / (b-2)) of the constituent unit (b-1) to the constituent unit (b-2) in the block B is 26 / 74-74 / 26.

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 that can solve the above-mentioned problems is a block copolymer having an A block and a B block, characterized in that the A block does not substantially contain a structural unit (b-2) having a basic group, the B block contains a structural unit (b-1) having a chain hydrocarbon group and a structural unit (b-2) having a basic group, the molar volume ratio of the structural unit (b-1) to the structural unit (b-2) ((b-1) / (b-2)) is 0.10 to 1.10, and the molar ratio of the structural unit (b-1) to the structural unit (b-2) in the B block ((b-1) / (b-2)) is 26 / 74 to 74 / 26.

[0013] The block copolymer of the present invention is designed to have a high affinity between its A block and the dispersion medium, and a high affinity between its B block and the coloring material, and the basic group introduced in the B block is adsorbed on the coloring material. Here, by setting the molar ratio of the structural unit (b-1) and the structural unit (b-2) in the B block within a specified range, the interval of the basic group introduced can be adjusted. In addition, by setting the molar volume ratio ((b-1) / (b-2)) within a specified range, the steric hindrance to the basic group can be controlled. Therefore, the basic group introduced in the B block is easily adsorbed on the coloring material, and the dispersibility of the coloring material is 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, the viscosity of a coloring composition can be reduced. 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 block and a B block. In the present specification, "A block" is interchangeable with "A segment", and "B block" is interchangeable with "B segment". 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 acryl 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] (Block A)

[0022] The A block is a block that does not substantially contain a structural unit (b-2) having a basic group. As structural units constituting the A block, structural units derived from (meth)acrylic monomers and structural units derived from vinyl monomers other than (meth)acrylic monomers can be listed. The structural units constituting the A block may be only one type or may have two or more types.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] Specific examples of the (meth)acrylate having an alkoxyalkyl group include methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate.

[0037] 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.

[0038] 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.

[0039] Specific examples of the (meth)acrylic acid-based monomer having an amide group include N,N-dimethyl(meth)acrylamide and 4-(meth)acryloylmorpholine.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] Examples of the α-olefin include 1-hexene, 1-octene, and 1-decene.

[0045] 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.

[0046] Examples of the hydroxyl group-containing vinyl monomer include 4-vinylphenol and 4-hydroxybutyl vinyl ether.

[0047] Examples of the heterocyclic ring-containing vinyl monomer include 2-vinylthiophene, N-methyl-2-vinylpyrrole, and 1-vinyl-2-pyrrolidone.

[0048] Examples of the vinyl amide include N-vinylformamide, N-vinylacetamide, and N-vinyl-ε-caprolactam.

[0049] Examples of the vinyl carboxylate include vinyl acetate, vinyl pivalate, and vinyl benzoate.

[0050] Examples of the dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, and 7-methyl-1,6-octadiene.

[0051] 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.

[0052] 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 %.

[0053] The A block 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.

[0054] As a structural unit derived from a (meth) acrylic acid-based monomer, the A block 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 block, 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.

[0055] As the structural unit derived from the (meth)acrylate having a lactone-modified hydroxyl group, a structural unit represented by formula (4) is preferred.

[0056]

[0057] [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.]

[0058] In the formula (4), n1 is preferably an integer of 1-7, and more preferably an integer of 1-5.

[0059] 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.

[0060] 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.

[0061] When the A block 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 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, in 100 mol% of the structural units constituting the A block. 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.

[0062] When the A block contains a structural unit derived from a (meth)acrylate having a lactone-modified hydroxyl group, the content thereof is preferably 0.5 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, particularly preferably 30 mol% or more, preferably 95 mol% or less, more preferably 70 mol% or less, and further preferably 40 mol% or less in 100 mol% of the structural units constituting the A block. By setting the content of the structural unit derived from the (meth)acrylate having a lactone-modified hydroxyl group within the above range, the resolubility of the coloring composition containing the block copolymer can be improved.

[0063] The A block 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 its proportion becomes more, the affinity with the dispersion medium and the binder resin may become lower. 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. It should be noted that the A block may not contain a structural unit from a vinyl monomer having an acidic group.

[0064] When a structural unit derived from a 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 block. 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.

[0065] The A block does not substantially contain a structural unit (b-2) having a basic group. That is, the monomers constituting the A block preferably do not contain a monomer having a basic group. If there is a basic group in the A block, when used as a dispersant, the coloring material is adsorbed on both the A block and the B block, 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 block 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%.

[0066] When the A block contains two or more structural units, the various structural units contained in the A block may be contained in the A block in any form such as random copolymerization or block copolymerization. From the viewpoint of uniformity, it is preferably contained in the form of random copolymerization. For example, the A block may be formed by a copolymer having structural units composed of the a1 block and structural units composed of the a2 block.

[0067] (B block)

[0068] The B block is a block containing a structural unit (b-1) having a chain hydrocarbon group and a structural unit (b-2) having a basic group.

[0069] (Structural unit having a chain hydrocarbon group (b-1))

[0070] The B block contains a structural unit (b-1) having a chain hydrocarbon group. Since the B block has the structural unit (b-1), it can interact well with the coloring material particles in the dispersion medium, thereby becoming a block copolymer showing excellent dispersibility. The structural unit (b-1) may be only one or may have two or more. 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 chain hydrocarbon group.

[0071] The structural unit (b-1) has a chain hydrocarbon group. Examples of the chain hydrocarbon group include a straight-chain alkyl group and a branched-chain alkyl group. The structural unit (b-1) does not have a basic group.

[0072] In the structural unit (b-1), the chain hydrocarbon group is introduced into the side chain part, and its position is more than two atoms away from the main chain. In this specification, the position of the hydrocarbon group more than two atoms away from the main chain refers to the position of the carbon atom on the polymer main chain bonded with the side chain is 0 (zero), and the position after the second atom of the side chain from this position is bonded with a hydrocarbon group. The atom on the side chain can also be an atom or substituent other than carbon. Specifically, for example, in the case of the following formula (X1), the chain hydrocarbon group X in the formula is located at a position two atoms away from the main chain.

[0073]

[0074] The structural unit (b-1) may be any structural unit as long as it does not have a basic group described below as a substituent and has a chain hydrocarbon group, and examples thereof include a structure derived from a vinyl monomer having a chain hydrocarbon group.

[0075] The structural unit (b-1) is preferably a structural unit represented by formula (1).

[0076]

[0077] [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 chain hydrocarbon group.]

[0078] The A 11 represents an ester group (-CO-O-), an amide group (-CO-NH-) or a single bond, and an ester group is preferred from the aspect of affinity with the dispersion medium or the binder resin. It should be noted that the bonding direction of the ester group and 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 .

[0079] As the R 12 Examples of the chain hydrocarbon group represented by include a straight-chain alkyl group and a branched-chain alkyl group.

[0080] 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.

[0081] 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.

[0082] Examples of the vinyl monomer that forms the structural unit represented by formula (1) include (meth)acrylates having a linear alkyl group, (meth)acrylates having a branched alkyl group, etc. Among them, (meth)acrylates having a linear alkyl group are preferred.

[0083] 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-stearyl (meth)acrylate.

[0084] 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, and isodecyl (meth)acrylate.

[0085] The molar volume of the structural unit (b-1) is preferably 50 cm 3 / mol or more, more preferably 60cm 3 / mol or more, more preferably 65cm 3 / mol or more, preferably 185cm 3 / mol or less, more preferably 130cm 3 / mol or less, more preferably 100cm 3 / mol or less. If the molar volume of the structural unit (b-1) is 50cm 3 / mol or more, the interaction with the coloring material particles is better. If the 3 / mol or less, the aggregation of the coloring material particles can be further suppressed.

[0086] The molar volume (V) of the structural unit is the sum of the molar volumes Vi of the atomic groups i constituting the structural unit. The molar volumes Vi of representative atomic groups are shown in Table 1.

[0087] Table 1

[0088]

[0089] The molar volume ratio ((b-1) / (b-2)) of the structural unit (b-1) to the structural unit (b-2) described later is 0.10 or more, preferably 0.30 or more, more preferably 0.60 or more, and 1.10 or less, preferably 1.00 or less, and more preferably 0.90 or less. If the molar volume ratio ((b-1) / (b-2)) is within the above range, the viscosity and yield value of the coloring composition become lower, and their stability is also better. It should be noted that when the B block has a plurality of structural units (b-1) and / or structural units (b-2), the average value of each molar volume is calculated, and the molar volume ratio ((b-1) / (b-2)) is calculated using the average value. The average value of the molar volume is obtained as follows: the molar volume of each structural unit is calculated, the molar volume of each structural unit is multiplied by the molar fraction of its 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 molar volume 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 molar volume 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 molar volume of structural unit (b-12).

[0090] The combination of the structural unit (b-1) and the structural unit (b-2) described later can also be examined using a material informatics method utilizing computational science / information science.

[0091] In 100 mol% of the structural units constituting the B block, the content of the structural unit (b-1) is preferably 26 mol% or more, more preferably 35 mol% or more, further preferably 40 mol% or more, particularly preferably 45 mol% or more, preferably 74 mol% or less, more preferably 65 mol% or less, further preferably 60 mol% or less, particularly preferably 55 mol% or less. When the content of the structural unit (b-1) is within the above range, the viscosity and yield value of the coloring composition are reduced, the stability is improved, and the heat resistance of the obtained coloring layer is improved.

[0092] (Structural unit having a basic group (b-2))

[0093] The B block contains a structural unit (b-2) having a basic group. The structural unit (b-2) provides high affinity with the coloring material. The structural unit (b-2) may be one type or two or more types.

[0094] 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 above.

[0095] Examples of the structural unit (b-2) include a structure derived from a vinyl monomer having a basic group.

[0096] As the structural unit (b-2), a structural unit represented by formula (2) is preferred.

[0097]

[0098] [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.]

[0099] The A 21 represents an ester group (-CO-O-), an amide group (-CO-NH-) or a single bond, and from the perspective of affinity with the dispersion medium or the binder resin, 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 .

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] Examples of the chain hydrocarbon group include a linear alkyl group and a branched alkyl group, and a linear alkyl group is preferred.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] Furthermore, the hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms.

[0117] 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.

[0118]

[0119] [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.]

[0120] 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.

[0121] The molar volume of the structural unit (b-2) is preferably 30 cm 3 / mol or more, more preferably 50cm 3 / mol or more, more preferably 100cm 3 / mol or more, preferably 200cm 3 / mol or less, more preferably 150cm 3 / mol or less, more preferably 140cm 3 / mol or less. If the molar volume of the structural unit (b-2) is 30cm 3 / mol or more, the interaction with the coloring material particles is better, and if it is 200cm 3 / mol or less, the aggregation of the coloring material particles can be further suppressed.

[0122] In 100 mol% of the structural units constituting the B block, the content of the structural unit (b-2) is preferably 26 mol% or more, more preferably 35 mol% or more, further preferably 40 mol% or more, particularly preferably 45 mol% or more, preferably 74 mol% or less, more preferably 65 mol% or less, further preferably 60 mol% or less, particularly preferably 55 mol% or less. When the content of the structural unit (b-2) is within the above range, the affinity with the coloring material is further improved.

[0123] The molar ratio ((b-1) / (b-2)) of the structural unit (b-1) to the structural unit (b-2) in the B block is preferably 26 / 74 or more, more preferably 37 / 63 or more, further preferably 40 / 60 or more, and preferably 74 / 26 or less, more preferably 70 / 30 or less, further preferably 55 / 45 or less. When the molar ratio ((b-1) / (b-2)) is 26 / 74 or more, the interaction with the coloring material particles is better, and when it is 74 / 26 or less, aggregation between the coloring material particles can be further suppressed.

[0124] In 100 mol% of the structural units constituting the B block, the total content ((b-1) + (b-2)) of the structural unit (b-1) and the structural unit (b-2) is preferably 52 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, and particularly preferably 90 mol% or more. If the total content ((b-1) + (b-2)) is 52 mol% or more, the interaction with the coloring material particles is better. The upper limit of the total content ((b-1) + (b-2)) is 100 mol%.

[0125] (Structural unit of salt having a basic group (b-3))

[0126] The B block may contain a salt structure unit (b-3) having a basic group in addition to the structure unit (b-1) and the structure unit (b-2). By having the structure unit (b-3), strong adsorption to the surface of the coloring material can be maintained for a long time, and storage stability is further improved. The structure unit (b-3) may be only one type or may have two or more types.

[0127] 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.

[0128] As the structural unit (b-3), a structural unit represented by formula (3) is preferred.

[0129]

[0130] [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.]

[0131] The A 31represents an ester group (-CO-O-), an amide group (-CO-NH-) or a single bond, and from the perspective of affinity with the dispersion medium or the binder resin, 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 .

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] Examples of the chain hydrocarbon group include a linear alkyl group and a branched alkyl group, and a linear alkyl group is preferred.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] Furthermore, the hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms.

[0150] R 33 , R 34 and R 35 Bonding to form a ring structure refers to R 33 , R34 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.

[0151]

[0152] [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.]

[0153] As X - Examples of the anion include halogen anions, carboxylate anions, sulfate anions, sulfonate anions, phosphate anions, and nitroxide anions.

[0154] Examples of the halogen anion include a fluoride anion, a chloride anion, a bromide anion, and an iodine anion.

[0155] Examples of the carboxylate anion include alkyl carboxylate anions such as acetate anion and propionate anion; and aromatic carboxylate anions such as benzoate anion.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] When the structural unit (b-3) is contained, the total content ((b-2) + (b-3)) of the structural unit (b-2) and the structural unit (b-3) in 100 mol% of the structural units constituting the B block is preferably 26 mol% or more, more preferably 35 mol% or more, further preferably 40 mol% or more, particularly preferably 45 mol% or more, preferably 74 mol% or less, more preferably 65 mol% or less, further preferably 60 mol% or less, particularly preferably 55 mol% or less. If the total content ((b-2) + (b-3)) is 26 mol% or more, the interaction with the coloring material particles is better, and if it is 74 mol% or less, the aggregation between the coloring material particles can be further suppressed.

[0161] When the structural unit (b-3) is contained, the molar ratio of the structural unit (b-2) to the structural unit (b-3) in the B block ((b-2) / (b-3)) is preferably 10 / 90 or more, more preferably 20 / 80 or more, and further preferably 35 / 65 or more, and preferably 90 / 10 or less, more preferably 80 / 20 or less, and further preferably 65 / 35 or less. When the molar ratio ((b-2) / (b-3)) is within the above range, strong adsorption to the surface of the coloring material can be maintained for a long time, and storage stability is further improved.

[0162] When the structural unit (b-3) is contained, the molar ratio of the structural unit (b-1) to the total amount of the structural unit (b-2) and the structural unit (b-3) in the B block ((b-1) / {(b-2)+(b-3)}) is preferably 26 / 74 or more, more preferably 30 / 70 or more, and further preferably 35 / 65 or more, and is preferably 74 / 26 or less, more preferably 70 / 30 or less, and further preferably 65 / 35 or less. When the molar ratio ((b-1) / {(b-2)+(b-3)}) is 26 / 74 or more, the interaction with the coloring material particles is better, and when it is 74 / 26 or less, aggregation between the coloring material particles can be further suppressed.

[0163] The B block may contain other structural units (b-4) in addition to the structural units (b-1), (b-2) and (b-3). Specific examples of vinyl monomers that can form other structural units (b-4) of the B block include the same monomers as those exemplified as specific examples of monomers that form the structural units of the A block.

[0164] When the structural unit (b-4) is contained, the content of the structural unit (b-4) in 100 mol% of the structural units constituting the B block is preferably 2.0 mol% or less, more preferably 0.5 mol% or less, and further preferably 0.05 mol% or less.

[0165] The structural unit (b-4) can be divided into: a structural unit (b-41) whose molar volume ratio ((b-4) / (b-2)) relative to the structural unit (b-2) is less than 1.10, and a structural unit (b-42) whose molar volume ratio ((b-4) / (b-2)) relative to the structural unit (b-2) is greater than 1.10.

[0166] When the B block contains the structural unit (b-42), the content thereof is preferably 2.0 mol% or less, more preferably 1.0 mol% or less, and further preferably 0.5 mol% or less in 100 mol% of the structural units constituting the B block. When the content of the structural unit (b-42) in the B block is within the above range, the steric hindrance to the basic group can be reduced, and the basic group is more easily adsorbed to the coloring material.

[0167] 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. For example, the B block may be formed by a copolymer having structural units composed of the b1 block and structural units composed of the b2 block.

[0168] (Block Copolymer)

[0169] 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 viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, when the A block is represented by A and the B block 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 at least one structure of the copolymer. Among them, from the viewpoint of operability during processing and physical properties of the composition, AB type diblock copolymers are preferred. It is believed that by constituting an AB type diblock copolymer, the structural units of the A block and the structural units (b-2) of the B block 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 besides the A block and the B block.

[0170] The total molar content of the structural units constituting the A block in the total structural units constituting the block copolymer is preferably 5 mol% or more, more preferably 20 mol% or more, further preferably 40 mol% or more, and preferably 98 mol% or less, more preferably 80 mol% or less, further preferably 60 mol% or less.

[0171] The total molar content of the structural units constituting the B block in the total structural units constituting the block copolymer is preferably 2 mol% or more, more preferably 20 mol% or more, further preferably 40 mol% or more, and preferably 95 mol% or less, more preferably 80 mol% or less, further preferably 60 mol% or less.

[0172] In the block copolymer, the molar ratio of the total molar amount of the structural units constituting the A block to the total molar amount of the structural units constituting the B block (A block / B block) is preferably 30 / 70 or more, more preferably 40 / 60 or more, further preferably 45 / 55 or more, preferably 85 / 15 or less, more preferably 70 / 30 or less, further preferably 60 / 40 or less, and particularly preferably 55 / 45 or less. When the molar ratio (A block / B block) is 30 / 70 or more, the adsorption of the coloring material particles is better, and when it is 85 / 15 or less, the dispersion in the dispersion medium is better due to the steric repulsion caused by the dispersant adsorbed on the coloring material particles.

[0173] 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").

[0174] 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 1.5. If the molecular weight distribution (Mw / Mn) is less than 3.0, the dispersion performance 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.

[0175] 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 55 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.

[0176] 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.

[0177] (Method for preparing block copolymer)

[0178] The preparation method of the block copolymer includes the following methods: a method of first preparing an A block by a polymerization reaction of a vinyl monomer, and then polymerizing a monomer of a B block on the A block; a method of first preparing a B block, and then polymerizing a monomer of an A block on the B block; a method of preparing an A block and a B block separately, and then coupling the A block and the B block; a method of first preparing an A block, and then polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit (b-1) and a structural unit (b-2) on the A block, 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 an A block on the polymer, and quaternizing a part of the tertiary amine structure of the structural unit (b-2) in the obtained polymer; a method for separately preparing an A block and a block having structural units (b-1) and structural units (b-2), coupling these blocks, and then quaternizing a part of the tertiary amine structure of the structural unit (b-2) in the obtained polymer.

[0179] 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.

[0180] 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.

[0181] 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.

[0182] Specific examples of the TERP polymerization method include the following (a) to (d).

[0183] (a) A method of polymerizing a vinyl monomer using an organic tellurium compound represented by formula (6).

[0184] (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.

[0185] (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).

[0186] (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).

[0187]

[0188] [In formula (6), R 61 represents 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 64represents 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.]

[0189] 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.

[0190] 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.

[0191] 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] <Dispersant>

[0197] 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 block) 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 the type of the dispersed coloring material is not particularly limited.

[0198] The dispersant of the present invention can not only improve the dispersibility of the coloring material but also improve the heat resistance, and therefore can be suitably used as a dispersant for a coloring composition for a color filter.

[0199] 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.

[0200] 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.

[0201] <Coloring Composition>

[0202] The coloring composition of the present invention contains the above-mentioned dispersant, coloring material, and dispersion medium. The coloring composition of the present invention is excellent not only in the dispersion performance of the coloring material but also in the heat resistance, and thus can be suitably used as a coloring composition for color filters.

[0203] (Coloring material)

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] 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.

[0210] (Dispersion Medium)

[0211] 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. ;

[0212] 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.

[0213] 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.

[0214] (Binder resin)

[0215] 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.

[0216] 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.

[0217] (Alkali soluble resin)

[0218] 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.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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.

[0223] 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.

[0224] 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.

[0225] 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.

[0226] 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.

[0227] (Polymerizable compound)

[0228] 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.

[0229] 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.

[0230] 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.

[0231] (Thermosetting resin, thermoplastic resin)

[0232] 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.

[0233] (Photopolymerization Initiator)

[0234] 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.

[0235] 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.

[0236] 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.

[0237] (Other ingredients)

[0238] 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.

[0239] 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.

[0240] Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-tert-butyl-p-cresol, and β-naphthol.

[0241] 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.

[0242] 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.

[0243] Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.

[0244] Examples of the amphoteric surfactant include betaine compounds, imidazolium salts, imidazolines, and amino acids.

[0245] Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dioctanoate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and glyceryl triacetate.

[0246] 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.

[0247] 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.

[0248] <Method for preparing coloring composition>

[0249] 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.

[0250] <Color filter>

[0251] The color filter of the present invention includes a colored layer formed using the above-mentioned colored composition.

[0252] 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.

[0253] 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.

[0254] 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.

[0255] 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.

[0256] Example

[0257] The present invention is further described in detail below based on specific examples. The present invention is not limited by 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 of the block copolymer, and the physical properties of the coloring composition and the coating film are evaluated according to the following methods.

[0258] [Evaluation method]

[0259] In addition, the meanings of the abbreviations are as follows: 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, HEMA: 2-hydroxyethyl methacrylate, MMA: methyl methacrylate, EMA: ethyl methacrylate, BMA: n-butyl methacrylate, HMA: n-hexyl methacrylate, CHMA: cyclohexyl methacrylate, DMAEMA: dimethylaminoethyl methacrylate, DMAPMAm: dimethylaminopropyl methacrylamide, PMA: propylene glycol monomethyl ether acetate.

[0260] (Polymerization rate)

[0261] 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.

[0262] (Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn))

[0263] 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 20 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.

[0264] (Amine value)

[0265] 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.

[0266] B=56.11×Vs×0.1×f / w

[0267] 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 measurement sample (g) (solid content conversion value).

[0268] (Zeta potential measurement)

[0269] The zeta potential (mV) was calculated by obtaining the mobility of the coloring material (pigment particles) using a zeta potential, particle size, and molecular weight measurement system (manufactured by Otsuka Electronics, "ELSZ-2000ZS"). In addition, Tables 4 and 5 show the difference between the zeta potential of the coloring composition and the zeta potential of the coloring material dispersion liquid not containing a dispersant (Δzeta potential (=zeta potential of the coloring composition - zeta potential of the coloring material dispersion liquid)).

[0270] The coloring material concentration of the coloring material dispersion liquid not containing a dispersant is the same as the coloring material concentration of the coloring composition as a comparative object.

[0271] The zeta potential of the coloring composition and coloring material dispersion liquid just prepared was measured.

[0272] (Initial viscosity, viscosity after storage)

[0273] 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).

[0274] The initial viscosity of the coloring composition immediately after preparation and the viscosity after storage at 40° C. for one week were measured.

[0275] (Initial yield value, yield value after storage)

[0276] The viscosity (mPa·s) was measured using an E-type viscometer (trade name: RE-80L, manufactured by Toki Sangyo) with a conical rotor (0.8°×R24) at 25° C. while changing the rotor speed, and the yield value was calculated using the Casson equation.

[0277] The initial yield value of the coloring composition immediately after preparation and the yield value after storage at 40° C. for one week were measured.

[0278] (PMA resolubility)

[0279] Specifically, the colored composition was applied on a glass plate (1 mm thick, 100 mm on each side) using a spin coater (MS-150A manufactured by MIKASA) at 2000 rpm for 10 seconds, and dried at 90° C. for 2 minutes to form a colored layer.

[0280] The glass plate with the colored layer formed thereon was immersed in the PMA solution for 24 hours, and the absorbance of the solution was measured using a spectrophotometer (Hitachi, U3900 / 3900H spectrophotometer). The higher the absorbance, the better the resolubility of PMA.

[0281] (Heat resistance)

[0282] A diluted solution of the coloring composition adjusted to 40% NV (non-volatile component concentration) was applied to a glass substrate at 2000 rpm for 10 seconds using a spin coater (manufactured by MIKASA, "MS-150A").

[0283] The coating film was softened at 90°C for 10 minutes to form a colored layer. The b * Next, the coloring layer was subjected to a heat treatment by formal baking at 230°C for 30 minutes, and the b value of the coloring layer after the heat treatment was measured. * Value. b of the coloring layer * The value was measured using a spectrophotometer (manufactured by Konica Minolta, Japan, model CM-5) with regular reflected light removed. * The value of b after heat treatment * The difference between the values ​​(Δb * = After heat treatment b * Value-after heat treatment * The smaller the difference, the better the heat resistance.

[0284] <Synthesis of Block Copolymer>

[0285] (Block copolymer No. 1)

[0286] In a flask equipped with an argon inlet and a stirrer, 4.4 g of BMA, 13.3 g of CL5MA, 0.11 g of AIBN, and 11.8 g of PMA were added, and after nitrogen substitution, 1.00 g of BTEE and 0.62 g of DBDT were added, and the A block was polymerized at 60° C. for 25 hours. The polymerization rate was 99.0%.

[0287] A mixed solution of 5.6 g of DMAEMA, 5.1 g of BMA, 0.06 g of AIBN and 7.1 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 24 hours to polymerize the B block. The polymerization rate was 98.0%.

[0288] 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 14,683, an Mw / Mn of 1.21, and an amine value of 66 mgKOH / g.

[0289] (Block copolymer No. 2 to 12)

[0290] Block copolymers No. 2 to 12 were prepared in the same manner as the preparation method of block copolymer No. 1. Table 2 shows the monomers used, organic tellurium compounds (BTEE), organic ditellurium compounds (DBDT), azo polymerization initiators (AIBN), solvents (PMA), reaction temperature, reaction time, and polymerization rate. In addition, Tables 4 and 5 show the composition, Mw, Mw / Mn, and amine 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.

[0291] Table 2

[0292]

[0293] (Coloring Composition Nos. 1 to 14)

[0294] The block copolymers No. 1 to 12 obtained above were used to prepare a coloring composition. Specifically, each component was added to a bead mill (trade name: DISPERMAT CA, manufactured by VMA-GETZMANN GmbH) according to the ratio shown in Table 3 (coloring material concentration 12%), and zirconium oxide beads were further added. The mixture was stirred for 2 hours. After the stirring was completed, the beads were filtered off to prepare coloring compositions No. 1 to 14. In addition, coloring material dispersions (Red 254, Green 59) were prepared in the same manner using only the coloring material and the solvent.

[0295] Table 3

[0296]

[0297] Red 254: CI Pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals)

[0298] Green 59: CI Pigment Green 59 (trade name: FASTOGEN (registered trademark) GREEN C100, manufactured by DIC)

[0299] The zeta potential of the obtained coloring compositions No. 1 to 14 and the coloring material dispersion was measured, and the Δzeta potential was calculated. The coloring composition was diluted with a solvent (PMA), the coloring material concentration was adjusted to 6%, and the viscosity was measured. In addition, for coloring compositions No. 1 and 9, the PMA resolubility and heat resistance of the coloring layer formed by the coloring composition were also evaluated. The results are shown in Tables 4 and 5.

[0300] Table 4

[0301]

[0302] Table 5

[0303]

[0304] The A blocks of block copolymers No. 1 to 4 and 11 substantially do not contain a structural unit (b-2) having a basic group, and the B blocks contain a structural unit (b-1) having a chain hydrocarbon group and a structural unit (b-2) having a basic group, and the molar volume ratio ((b-1) / (b-2)) is 0.10 to 1.10, and the molar ratio ((b-1) / (b-2)) is 26 / 74 to 74 / 26.

[0305] Coloring compositions Nos. 1 to 4, 11 and 13 using these block copolymers Nos. 1 to 4 and 11 as dispersants all had high Δζ potentials, low initial viscosities, and low viscosities after storage, and had high dispersibility of the coloring material.

[0306] Block copolymer No. 5 has a molar volume ratio ((b-1) / (b-2)) of more than 1.10. Coloring composition No. 5 using block copolymer No. 5 has high initial viscosity and high viscosity after storage.

[0307] Block copolymer No. 6 is a case where the B block contains a structural unit having a cyclic hydrocarbon group instead of the structural unit (b-1) having a chain hydrocarbon group. Coloring composition No. 6 using this block copolymer No. 6 has a low Δζ potential and poor dispersibility of the coloring material.

[0308] Block copolymer No. 7 is a case where the molar ratio ((b-1) / (b-2)) is larger than 74 / 26. Coloring composition No. 7 using this block copolymer No. 7 has a low Δζ potential and poor dispersibility of the coloring material.

[0309] Block copolymers Nos. 8 to 10 and 12 have a molar ratio ((b-1) / (b-2)) of less than 26 / 74. Coloring compositions Nos. 8 to 10 and 14 using these block copolymers Nos. 8 to 10 and 12 have high initial viscosity and high viscosity after storage.

[0310] Coloring compositions No. 11 and 12 are the cases where CI Pigment Green 59 is used as a coloring material and block copolymer No. 4 or 10 is used as a dispersant. In comparison, coloring composition No. 11 using block copolymer No. 4 has a low initial viscosity and a low viscosity after storage, and the dispersibility of the coloring material is high. Therefore, it can be seen that the block copolymer of the present invention has improved dispersibility regardless of the type of coloring material.

[0311] The present invention includes the following embodiments.

[0312] (Implementation 1) A block copolymer comprising an A block and a B block, wherein the A block substantially does not contain a structural unit (b-2) having a basic group, the B block contains a structural unit (b-1) having a chain hydrocarbon group and a structural unit (b-2) having a basic group, the molar volume ratio of the structural unit (b-1) to the structural unit (b-2) ((b-1) / (b-2)) is 0.10 to 1.10, and the molar ratio of the structural unit (b-1) to the structural unit (b-2) in the B block ((b-1) / (b-2)) is 26 / 74 to 74 / 26.

[0313] (Embodiment 2) The block copolymer according to Embodiment 1, wherein the amine value of the block copolymer is 10 mgKOH / g to 150 mgKOH / g.

[0314] (Embodiment 3) The block copolymer according to Embodiment 1 or 2, wherein the structural unit (b-1) is a structural unit represented by formula (1).

[0315]

[0316] [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 chain hydrocarbon group.]

[0317] (Embodiment 4) The block copolymer according to any one of Embodiments 1 to 3, wherein the structural unit (b-2) is a structural unit represented by formula (2).

[0318]

[0319] [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 R24 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.]

[0320] (Embodiment 5) The block copolymer according to any one of Embodiments 1 to 4, 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 block is 80 mol % or more.

[0321] (Embodiment 6) A block copolymer according to any one of Embodiments 1 to 5, wherein the A block contains a structural unit derived from a (meth)acrylic monomer, and 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.

[0322] (Embodiment 7) The block copolymer according to any one of Embodiments 1 to 6, wherein the A block contains a structural unit (a-1) derived from a (meth)acrylate having a hydroxyl group.

[0323] (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 block is 26 mol % to 74 mol %.

[0324] (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 block to the total molar amount of the structural units constituting the B block (A block / B block) is 30 / 70 to 85 / 15.

[0325] (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.

[0326] (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.

[0327] (Embodiment 12) A dispersant characterized by containing the block copolymer according to any one of Embodiments 1 to 11.

[0328] (Embodiment 13) A coloring composition characterized by containing a coloring material, a dispersion medium and the dispersant described in Embodiment 12.

[0329] (Embodiment 14) The colored composition according to Embodiment 13, which is used for a color filter.

[0330] (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 block and a B block, characterized in that: The A block substantially does not contain a structural unit (b-2) having a basic group, The B block contains a structural unit (b-1) having a chain hydrocarbon group and a structural unit (b-2) having a basic group, The molar volume ratio of the structural unit (b-1) to the structural unit (b-2) ((b-1) / (b-2)) is 0.10 to 1.10, The molar ratio of the structural unit (b-1) to the structural unit (b-2) in the B block ((b-1) / (b-2)) is 26 / 74 to 74 / 26.

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

3. 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 It represents a chain hydrocarbon group.

4. 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.

5. 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 block is 80 mol % or more.

6. The block copolymer according to claim 1 or 2, wherein The A block contains a structural unit derived from a (meth)acrylic acid-based monomer, and the (meth)acrylic acid-based monomer is at least one 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.

7. The block copolymer according to claim 1 or 2, wherein The A block contains a structural unit (a-1) derived from a (meth)acrylate having a hydroxyl 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 block is 26 mol % to 74 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 block to the total molar amount of the structural units constituting the B block (A block / B block) is 30 / 70 to 85 / 15.

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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