Coloring composition and coating film

Abstract

To provide a coloring composition that can form a coating layer having excellent jet-black properties.SOLUTION: A coloring composition contains a black coloring material, a dispersant, and an aqueous dispersion medium. The dispersant contains a block copolymer that has an A block containing a constitutional unit represented by formula (1) and a B block containing a constitutional unit represented by formula (3) and a constitutional unit having a basic group. In the formula (3), R31 is an alicyclic hydrocarbon group, Z3 is O or NH, and R32 is a hydrogen atom or a methyl group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a coloring composition containing a black colorant, a dispersant, and an aqueous dispersion medium. [Background technology]

[0002] In recent years, in order to prevent air pollution, there has been a demand to reduce the amount of volatile organic compounds (VOCs) emitted from factories and businesses. For this reason, the switch to water-based paints has been considered for the paints used to paint the metal plates that make up the bodies of automobiles and other vehicles. In addition, automotive paints are required to have not only high levels of paint film performance, such as durability, acid resistance, car wash scratch resistance, and chipping resistance, but also higher transparency, color development, and other aspects of the finished appearance of the paint film than ever before.

[0003] The coloring materials used in paints generally have a hydrophobic surface. In addition, dispersants used in solvent-based colored paints have low solubility in water and poor dispersion stability in aqueous dispersion media. In particular, carbon particles such as carbon black used as black coloring materials have a small primary particle size and an extremely large specific surface area, and therefore have a very strong cohesive force. For this reason, it is difficult to disperse carbon particles uniformly in an aqueous dispersion medium, and even if dispersed, there is a problem that the particles aggregate.

[0004] Therefore, in paints that use carbon black as a black colorant, a technique for improving the dispersibility of carbon black has been proposed. For example, Patent Document 1 describes a paint with a DBP oil supply of 150 ml / 100 g or less, an average primary particle size of 15 nm or less, and a specific surface area of ​​500 m 2 The document describes a highly jet-black carbon black dispersion (when the coloring agent is a black coloring agent, the coloring agent is sometimes called jet-black) in which carbon black having a molecular weight of 1000 to 10000 / g or less and a pH in the acidic to neutral range is dispersed as fine particles in an aqueous medium using a dispersant. In this document, the dispersibility of carbon black is improved by controlling the physical properties of the carbon black (see Patent Document 1 (Claim 1, paragraphs 0019, 0021, 0024)).

[0005] Furthermore, Patent Document 2 describes (A) an aqueous coating composition containing (a) a polymerizable unsaturated monomer having a specific cationic functional group, (b) a polymerizable unsaturated monomer having a polyoxyalkylene chain, and (c) a copolymer of other polymerizable unsaturated monomers, (B) a pigment, and (C) an acid group- and hydroxyl group-containing acrylic resin (see Patent Document 1 (Claim 1, paragraph 0014)). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2008-285632 A [Patent Document 2] JP 2014-5399 A Summary of the Invention [Problem to be solved by the invention]

[0007] In water-based paints using carbon particles as a black coloring material, paints with improved dispersibility of the carbon particles have been proposed, but there is room for improvement in preventing the aggregation of the carbon particles. The present invention has been made in consideration of the above circumstances, and aims to provide a water-based coloring composition containing a black coloring material (especially carbon particles) that can improve the jet blackness of the coating film when applied. [Means for solving the problem]

[0008] The coloring composition of the present invention, which has been able to solve the above problems, contains a black colorant, a dispersant, and an aqueous dispersion medium, and is characterized in that the dispersant contains a block copolymer having an A block containing a structural unit represented by formula (1) and a B block containing a structural unit represented by formula (3) and a structural unit having a basic group.

[0009] [ka] In formula (1), n1 represents an integer of 2 to 30. 11 R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 12 R represents an alkylene group having 1 to 3 carbon atoms. 13 represents a hydrogen atom or a methyl group. 12 may be the same or different.

[0010] [ka] [In formula (3), R 31 represents an alicyclic hydrocarbon group. 3 represents O or NH. 32 represents a hydrogen atom or a methyl group.

[0011] In the block copolymer contained as a dispersant in the coloring composition of the present invention, the structural unit represented by formula (1) contained in the A block has high affinity with an aqueous dispersion medium, and the structural unit represented by formula (3) and the structural unit having a basic group contained in the B block are adsorbed to a black colorant. Therefore, the coloring composition of the present invention has high dispersibility of a black colorant and can form a coating film with excellent jet blackness. Effect of the Invention

[0012] The coloring composition of the present invention is an aqueous coloring composition containing a black coloring material (particularly carbon particles), and is capable of giving a coating film with excellent jet blackness. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] <Coloring composition> The colored composition of the present invention contains a dispersant (block copolymer), a black colorant, and an aqueous dispersion medium.

[0014] (Coloring material) The black colorant used in the present invention is not particularly limited, and can be a pigment or dye used as a black colorant in conventional paints, and is preferably a black pigment from the viewpoint of light resistance and heat resistance. Examples of black pigments include carbon black such as furnace black, channel black, acetylene black, thermal black, lamp black, and bone black; carbon nanotubes; carbon nanofibers; fullerene; natural graphite; graphite; perylene pigments; lactam pigments; titanium black; metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; composite oxides; metal sulfides; metal sulfates; and metal carbonates, and are preferably at least one type of carbon particles selected from the group consisting of carbon black and carbon nanotubes.

[0015] The primary particle size of the carbon particles is not particularly limited, but is preferably 5 nm to 100 nm. The specific surface area of ​​the carbon particles is 300m 2 / g~1300m 2 / g is preferred, and 400m 2 / g~800m 2 The specific surface area is measured in accordance with JIS K 6217-3 (2001).

[0016] The DBP (dibutyl phthalate) oil absorption of the carbon particles is preferably 50 ml / 100 g to 150 ml / 100 g, and more preferably 80 ml / 100 g to 120 ml / 100 g. The DBP oil absorption is measured according to JIS K 6217-4 (2017).

[0017] The carbon particles may be subjected to an oxidation treatment on the surface. By performing the oxidation treatment, a carboxy group or a phenolic hydroxy group can be added to the surface of the carbon particles. The oxidation treatment can be performed by treating the surface of the carbon particles with ozone, nitric acid, or the like. The carbon particles having a carboxy group or a phenolic hydroxy group added to the surface have an acidic pH.

[0018] The carbon particles preferably have a pH of 3 to 9, and more preferably 5 to 9, when 1 g of the carbon particles is dispersed in 100 ml of water (25° C.).

[0019] A colorant other than black may be contained for adjusting the hue, etc., within a range that does not impair the preferred physical properties of the present invention.

[0020] The other coloring materials are not particularly limited, and pigments and dyes used as coloring materials in conventional paints can be used, with pigments being preferred from the viewpoints of light resistance and heat resistance. As the pigment, either an organic pigment or an inorganic pigment may be used, but an organic pigment containing an organic compound as a main component is preferred.

[0021] Examples of organic pigments include pigments of various colors such as blue pigments, red pigments, yellow pigments, green pigments, purple pigments, orange pigments, etc. Examples of the structure of the organic pigment include azo pigments such as phthalocyanine pigments, monoazo pigments, diazo pigments, and condensed diazo pigments, and polycyclic pigments such as diketopyrrolopyrrole pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments.

[0022] The coloring composition may contain only one type of other colorant, or may contain multiple types of other colorants.

[0023] Specific examples of blue pigments, according to compounds classified as pigments in the Color Index (CI), include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 17, 17:1, 19, 22, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 80, and the like. As the phthalocyanine pigment, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 17:1, and 75 are preferred, and as the copper phthalocyanine pigment and the monohalogenated copper phthalocyanine pigment, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, and 17:1 are preferred. As the anthraquinone pigment, CI Pigment Blue 60 is preferred. As the dioxazine pigment, CI Pigment Blue 80 is preferred.

[0024] Red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60 , 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 215, 216, 221, 224, 230, 231, 232, 233, 235, 236, 2 37, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 291, etc.

[0025] Yellow pigments include CI Pigment Yellow 1, 1; 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 60, 61, 62, 62:1, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136 , 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 213, 215, and the like.

[0026] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, aluminum phthalocyanine, polyhalogenated aluminum phthalocyanine, aluminum phthalocyanine hydroxide, diphenoxyphosphinyloxyaluminum phthalocyanine, diphenylphosphinyloxyaluminum phthalocyanine, polyhalogenated diphenoxyphosphinyloxyaluminum phthalocyanine, polyhalogenated diphenylphosphinyloxyaluminum phthalocyanine, and the like.

[0027] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0028] Examples of orange pigments include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 78, and 79.

[0029] Examples of inorganic pigments include barium sulfate, lead sulfate, titanium oxide (rutile type, anatase type, etc.), yellow lead, red iron oxide, and chromium oxide.

[0030] The number average particle diameter of the pigment is not particularly limited and may be appropriately selected depending on the application. From the viewpoint of high brightness, the coloring composition preferably contains a pigment having a number average particle diameter of 10 nm to 150 nm.

[0031] The pigment may contain a dye derivative as a dispersing aid. The dye derivative preferably contains an acidic dye derivative having an acidic group in order to form an ionic bond with a basic group (e.g., an amino group) in the block copolymer contained in the dispersant and adsorb it. This dye derivative is one in which an acidic group has been introduced into the dye skeleton. The dye skeleton is preferably the same or similar to the pigment constituting the coloring composition, or the same or similar to the compound that is the raw material of the pigment. Specific examples of the dye skeleton include an azo-based dye skeleton, a phthalocyanine-based dye skeleton, an anthraquinone-based dye skeleton, a triazine-based dye skeleton, an acridine-based dye skeleton, and a perylene-based dye skeleton. The acidic group introduced into the dye skeleton is preferably a carboxy group, a phosphoric acid group, or a sulfonic acid group. For convenience of synthesis and strength of acidity, a sulfonic acid group is preferred. The acidic group may be directly bonded to the dye skeleton, or may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, an ether, a sulfonamide, or a urethane bond.

[0032] The amount of the dye derivative used is not particularly limited, but is preferably 4 parts by mass to 17 parts by mass with respect to 100 parts by mass of the pigment, for example.

[0033] The upper limit of the content of the coloring material in the coloring composition is usually 80 mass%, preferably 70 mass%, and more preferably 60 mass% in the total solid content of the coloring composition from the viewpoint of brightness. The lower limit of the content of the coloring material in the coloring composition is usually 3 mass%, preferably 20 mass%, and more preferably 30 mass% in the total solid content of the coloring composition. Here, the solid content refers to components other than the dispersion medium described below.

[0034] The content of the dispersant relative to the colorant in the coloring composition is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, relative to 100 parts by mass of the colorant, and is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 80 parts by mass or less.

[0035] (Dispersant) The dispersant used in the present invention contains a block copolymer having an A block containing a structural unit represented by formula (1) and a B block containing a structural unit represented by formula (3) and a structural unit having a basic group. The dispersant contains the block copolymer as a main component (50% by mass or more), preferably contains the block copolymer in an amount of 75% by mass or more, and more preferably is composed only of the block copolymer. The block copolymer is considered to exert an effect of increasing the dispersibility of the black colorant, for example, by the alicyclic hydrocarbon group in the structure (B block) being firmly bonded to the hydrophobic surface of the colorant, and the B block being adsorbed to the black colorant (e.g., carbon particles).

[0036] The dispersant can be made into a dispersant solution before preparing the coloring composition, which makes it easier to disperse the black colorant (e.g., carbon particles). The solvent used in the dispersant solution is preferably a solvent that can dissolve the dispersant, does not react with these components, and has moderate volatility. The solvent can be, for example, a dispersion medium used in the coloring composition described later. The content of the solvent in the dispersant solution is not particularly limited and can be appropriately adjusted. The upper limit of the content of the solvent in the dispersant solution is usually 99% by mass. In addition, the lower limit of the content of the dispersion medium in the dispersant solution is usually 10% by mass, and preferably 30% by mass, in consideration of the viscosity suitable for producing the coloring composition described later.

[0037] (Block Copolymer) In the present invention, the "A block" can be rephrased as the "A segment", and the "B block" can be rephrased as the "B segment". In the present invention, the "vinyl monomer" refers to a monomer having a radically polymerizable carbon-carbon double bond in the molecule. The "structural unit derived from a vinyl monomer" refers to a structural unit in which the radically polymerizable carbon-carbon double bond of a vinyl monomer is polymerized to become a carbon-carbon single bond. "(Meth)acrylic" refers to "at least one of acrylic and methacrylic". "(Meth)acrylate" refers to "at least one of acrylate and methacrylate". "(Meth)acryloyl" refers to "at least one of acryloyl and methacryloyl".

[0038] (A Block) The A block is a block containing a structural unit represented by formula (1). The A block may have only one type of structural unit represented by formula (1), or may have two or more types of structural units.

[0039] [ka] In formula (1), n1 represents an integer of 2 to 30. 11 R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 12R represents an alkylene group having 1 to 3 carbon atoms. 13 represents a hydrogen atom or a methyl group. 12 may be the same or different.

[0040] In the formula (1), n1 is 2 or more, preferably 5 or more, and 30 or less, preferably 20 or less, more preferably 15 or less.

[0041] R 11 The alkyl group having 1 to 3 carbon atoms represented by the formula (I) may be either linear or branched, but is preferably linear. 11 Specific examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

[0042] R 12 The alkylene group having 1 to 3 carbon atoms represented by may be either linear or branched, but is preferably linear. 12 Specific examples of the alkylene group having 1 to 3 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a trimethylene group, and a propane-1,2-diyl group. 12 is preferably an ethylene group or a trimethylene group.

[0043] Examples of the monomer constituting the structural unit represented by formula (1) include (meth)acrylates having a polyalkylene glycol structure. The polyalkylene glycol portion may be, for example, a mixture of ethylene oxide and propylene oxide. Examples of the (meth)acrylates having a polyalkylene glycol structure include (meth)acrylates having a polyethylene glycol structure such as polyethylene glycol (degree of polymerization = 2-30) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization = 2-30) ethyl ether (meth)acrylate, and polyethylene glycol (degree of polymerization = 2-30) propyl ether (meth)acrylate; and (meth)acrylates having a polypropylene glycol structural unit such as polypropylene glycol (degree of polymerization = 2-30) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization = 2-30) ethyl ether (meth)acrylate, and polypropylene glycol (degree of polymerization = 2-30) propyl ether (meth)acrylate.

[0044] The content of the structural unit represented by formula (1) is preferably 20% by mass or more, more preferably 35% by mass or more, and even more preferably 50% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less, in 100% by mass of the A block. If the content is 20% by mass or more, the affinity with the aqueous dispersion medium is further improved, and if it is 95% by mass or less, the affinity with the coating film-forming resin is further improved.

[0045] It is preferable that the A block further contains a structural unit represented by formula (2). The structural unit represented by formula (2) in the A block may be of only one type, or may have two or more types. When the A block contains the structural unit represented by formula (2), the affinity with the coating film-forming resin is further improved.

[0046] [ka] [In formula (2), R 21R represents a chain hydrocarbon group which may have a substituent. 22 represents a hydrogen atom or a methyl group.

[0047] R 21 Examples of the chain-like hydrocarbon group represented by the formula (I) include linear alkyl groups and branched alkyl groups. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. Examples of the linear alkyl group include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-nonyl, n-decyl, and n-lauryl groups. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms. Examples of the branched alkyl group include isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, neopentyl, and isooctyl groups.

[0048] R 21 The substituents of the chain hydrocarbon group represented by the formula (I) include halogen groups, alkoxy groups, and benzoyl groups (-COC 6 H 5 ), hydroxyl groups, etc.

[0049] Examples of the vinyl monomer that forms the structural unit represented by formula (2) include (meth)acrylates having a chain alkyl group (straight-chain alkyl group or branched-chain alkyl group), (meth)acrylates having an aromatic group, etc. Among these, (meth)acrylates having a chain alkyl group (straight-chain alkyl group or branched-chain alkyl group) are preferred.

[0050] 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, decyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate.

[0051] 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.

[0052] Examples of the aromatic group include an aryl group, and may also 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, and phenoxyethyl (meth)acrylate.

[0053] When the structural unit represented by formula (2) is contained, the content thereof is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, and is preferably 80% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 50% by mass or less, in 100% by mass of the A block. If the content is 5% by mass or more, the affinity with the coating film-forming resin is further improved, and if it is 80% by mass or less, the affinity with the aqueous dispersion medium is further improved.

[0054] The A block may be composed of only the structural unit represented by formula (1), or may be composed of only the structural unit represented by formula (1) and the structural unit represented by formula (2), or may contain other structural units. The total content of the structural unit represented by formula (1) and the structural unit represented by formula (2) in the A block is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0055] Specific examples of vinyl monomers that can form other structural units of the A block include (meth)acrylates having a hydroxy group, (meth)acrylates having a lactone-modified hydroxy group, (meth)acrylates having an alkoxy group, (meth)acrylates having an acidic group, (meth)acrylic acid, and (meth)acrylates having a cyclic ether group.

[0056] Examples of (meth)acrylates having a hydroxy 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. Among these, (meth)acrylates having a hydroxyalkyl group having 1 to 5 carbon atoms are more preferred.

[0057] Examples of the (meth)acrylate having a lactone-modified hydroxyl group include (meth)acrylates having the above-mentioned hydroxyl group to which lactone has been added, and those having caprolactone are preferred. The amount of caprolactone added is preferably 1 mol to 20 mol, and more preferably 1 mol to 10 mol. Examples of the (meth)acrylate having a lactone-modified hydroxyl group include 1 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 2 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 3 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 4 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 5 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, and 10 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate.

[0058] Examples of the (meth)acrylate having an alkoxy group include methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate.

[0059] The acidic groups include carboxyl groups (-COOH) and sulfonic acid groups (-SO 3 H), phosphate group (-OPO 3 H 2 ), phosphonic acid group (-PO 3 H 2 ), phosphinic acid group (-PO 2 H 2 Examples of the (meth)acrylate having an acidic group include a (meth)acrylate having a carboxy group, a (meth)acrylate having a phosphoric acid group, and a (meth)acrylate having a sulfonic acid group.

[0060] Examples of (meth)acrylates having a carboxy group include monomers obtained by reacting (meth)acrylates having a hydroxy group, such as carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, and 2-(meth)acryloyloxyethyl phthalate, with acid anhydrides, such as maleic anhydride, succinic anhydride, and phthalic anhydride. Examples of (meth)acrylates having a phosphoric acid group include 2-(phosphonooxy)ethyl (meth)acrylate. Examples of (meth)acrylates having a sulfonic acid group include ethyl sulfonate (meth)acrylate.

[0061] Examples of (meth)acrylates having a cyclic ether group include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 2-[(2-tetrahydropyranyl)oxy]ethyl (meth)acrylate, and 1,3-dioxane-(meth)acrylate.

[0062] It is preferable that the A block does not substantially contain a structural unit represented by formula (3) described later, a structural unit having a basic group, and a structural unit having a basic group that forms a salt. That is, the content of the structural unit represented by (3), the structural unit having a basic group, and the structural unit having a basic group that forms a salt is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, in 100% by mass of the A block, and it is particularly preferable that the A block does not contain the structural unit represented by (3), the structural unit having a basic group, and the structural unit having a basic group that forms a salt.

[0063] When two or more types of structural units are contained in the A block, the various structural units contained in the A block may be contained in the A block in any form such as random copolymerization, block copolymerization, etc., and from the viewpoint of uniformity, it is preferable that they are contained in the A block in the form of random copolymerization. For example, the A block may be formed of a copolymer of structural units consisting of the a1 block and structural units consisting of the a2 block.

[0064] (Block B) The B block is a block containing a structural unit represented by the formula (3) and a structural unit having a basic group.

[0065] (Structural unit represented by formula (3)) The structural unit represented by formula (3) in the B block may be of only one type, or of two or more types.

[0066] [ka] [In formula (3), R 31 represents an alicyclic hydrocarbon group. 3 represents O or NH. 32 represents a hydrogen atom or a methyl group.

[0067] R 31 Examples of the alicyclic hydrocarbon group represented by the formula (1) include a cyclic alkyl group having a monocyclic structure and an alkyl group having a polycyclic structure. The alicyclic hydrocarbon group preferably has 4 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and further preferably 6 to 10 carbon atoms.

[0068] Examples of the cyclic alkyl group having a monocyclic structure include a cyclohexyl group, a methylcyclohexyl group, a cyclododecyl group, a 3,3,5-trimethylcyclohexyl group, a 4-tert-butylcyclohexyl group, etc. Examples of the alkyl group having a polycyclic structure include a bornyl group, an isobornyl group, a 1-adamantyl group, a 2-adamantyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a norbornyl group, a dicyclopentanyl group, a dicyclopentenyl group, etc.

[0069] Specific examples of the vinyl monomer that forms the structural unit represented by formula (3) include (meth)acrylates having a cyclic alkyl group with a monocyclic structure, and (meth)acrylates having a cyclic alkyl group with a polycyclic structure.

[0070] Examples of (meth)acrylates having a cyclic alkyl group with a monocyclic structure include compounds in which a cyclic alkyl group is directly bonded to a (meth)acryloyloxy group.Specific examples include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, and 4-tert-butylcyclohexyl (meth)acrylate.

[0071] Examples of (meth)acrylates having a cyclic alkyl group with a polycyclic structure include compounds in which a cyclic alkyl group with a bridged ring structure is directly bonded to a (meth)acryloyloxy group.Specific examples include bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate.

[0072] The content of the structural unit represented by formula (3) is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, and is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less, in 100% by mass of the B block. If the content is 15% by mass or more, the dispersibility of the coloring material is further improved, and if it is 80% by mass or less, an increase in the viscosity of the coloring composition can be suppressed.

[0073] (Structural unit having a basic group) The structural unit having a basic group may be a structural unit derived from a vinyl monomer having a basic group. The basic group is preferably an amino group in view of availability of raw materials and ease of synthesis. In this specification, the amino group refers to a general amino group structure (-NH 2 ) plus -NHR, where H is replaced by a hydrocarbon group. 41 , -NR 41 R 42 (R 41 , R 42 Each independently represents a chain or cyclic hydrocarbon group. 41 and R 42 may be bonded to each other to form a cyclic structure.) and nitrogen-containing heterocyclic groups (such as a pyridyl group and an imidazole group).

[0074] The structural unit having a basic group is preferably a structural unit represented by formula (4) or a structural unit represented by formula (5). The structural unit represented by formula (4) or the structural unit represented by formula (5) in the B block may be of one type or of two or more types.

[0075] [ka] [In formula (4), R 41 and R 42 R each independently represents a chain or cyclic hydrocarbon group which may have a substituent. 41 and R 42may be bonded to each other to form a ring structure. 43 represents a divalent hydrocarbon group. 4 represents O or NH. 44 represents a hydrogen atom or a methyl group.

[0076] R 41 and R 42 Examples of the chain-like hydrocarbon group represented by the formula (1) include linear alkyl groups and branched alkyl groups. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 10 carbon atoms, and even more preferably has 1 to 5 carbon atoms. Examples of the linear alkyl group include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-nonyl, n-decyl, and n-lauryl. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably has 3 to 10 carbon atoms, and even more preferably has 3 to 5 carbon atoms. Examples of the branched alkyl group include isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, neopentyl, and isooctyl.

[0077] R 41 and R 42 The substituents of the chain hydrocarbon group represented by the formula (I) include halogen groups, alkoxy groups, and benzoyl groups (-COC 6 H 5 ), hydroxyl groups, etc.

[0078] R 41 and R 42Examples of the cyclic hydrocarbon group represented by the formula (I) include a cyclic alkyl group and an aromatic group, and the cyclic alkyl group and the aromatic group may have a chain portion. The number of carbon atoms of the cyclic alkyl group is preferably 4 to 18, more preferably 6 to 12, and even more preferably 6 to 10. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The number of carbon atoms of the aromatic group is preferably 6 to 18, more preferably 6 to 12, and even more preferably 6 to 8. Examples of the aromatic group include a phenyl group, a tolyl group, a xylyl group, and a mesityl group. Examples 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.

[0079] R 41 and R 42 Examples of the substituent that the cyclic hydrocarbon group represented by the formula (I) has include a halogen group, an alkoxy group, a chain alkyl group, and a hydroxy group.

[0080] R 41 or R 42 Examples of the cyclic structure formed by bonding with each other include 5- to 7-membered nitrogen-containing heterocycles and condensed rings formed by condensing two of these. The nitrogen-containing heterocycle is preferably one that does not have aromaticity, and more preferably a saturated ring. Specific examples include structures represented by the following formulas (4-1), (4-2), and (4-3).

[0081] [ka] [In formulas (4-1), (4-2), and (4-3), R 45 represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5. m represents an integer of 0 to 4. n represents an integer of 0 to 4. * represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, multiple R 45 may be the same or different.

[0082] R 43 Examples of the divalent hydrocarbon group represented by the formula (I) include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, and an arenediyl group having 6 to 10 carbon atoms. Among these, an alkylene group having 1 to 10 carbon atoms is preferred. The alkylene group may be either linear or branched, but linear is preferred. The number of carbon atoms in the alkylene group is more preferably 1 to 4. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group.

[0083] Specific examples of vinyl monomers forming the structural unit represented by formula (4) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, ethylaminoethyl (meth)acrylate, ethylaminopropyl (meth)acrylate, ethylaminobutyl (meth)acrylate, propylaminoethyl (meth)acrylate, propylaminopropyl (meth)acrylate, propylaminobutyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide.

[0084] [ka] [In formula (5), R 81 , R 82 and R 83 R may be the same or different and represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. 84 represents a nitrogen-containing heterocyclic group. m8 represents an integer of 0 to 4.

[0085] R 81 ~R 83The number of carbon atoms in the alkyl group in R is preferably 1 to 6, and more preferably 1 to 4. The alkyl group is further preferably a methyl group or an ethyl group, and particularly preferably a methyl group. 81 ~R 83 The substituents in R are not particularly limited, but include a carboxy group, a sulfonic acid group, and esters and salts thereof; an amino group; and a hydroxy group. 81 ~R 83 is preferably a hydrogen atom.

[0086] R 84 Examples of the nitrogen-containing heterocyclic group represented by the formula: include a 4-pyridyl group, a 1-imidazole group, a 2-pyridyl group, a 9-carbazole group, and the like, with the 4-pyridyl group being preferred.

[0087] m8 is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and further preferably 0.

[0088] Examples of vinyl monomers forming the structural unit represented by formula (5) include 4-vinylpyridine, 4-allylpyridine, 4-(3-butenyl)pyridine, 1-vinyl-1H-imidazole, 1-allyl-1H-imidazole, 2-vinylpyridyl, 9-vinylcarbazole, etc. Among these, 4-vinylpyridine is preferred.

[0089] The content of the structural unit having a basic group is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, and is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less, in 100% by mass of the B block. If the content is 20% by mass or more, the dispersibility of the coloring material is further improved, and if it is 80% by mass or less, an increase in the viscosity of the color composition can be suppressed.

[0090] In the B block, the mass ratio of the structural unit represented by the formula (3) to the structural unit having a basic group (structural unit represented by the formula (3) / structural unit having a basic group) is preferably 0.15 or more, more preferably 0.2 or more, and even more preferably 0.4 or more, and is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.

[0091] The total content of the structural unit represented by formula (3) and the structural unit having a basic group is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, in 100% by mass of the block B. The block B may be composed only of the structural unit represented by formula (3) and the structural unit having a basic group.

[0092] In the structural unit having a basic group, a part of the basic group may form a salt. Examples of the salt of the basic group include inorganic salts such as halide salts (F, Cl, Br, I, etc.) and sulfate salts of the basic group; and sulfonates, sulfates, phosphates, or carboxylates of organic compounds. In view of the availability of raw materials and ease of synthesis, the salt of the basic group is preferably an amino group. In this specification, the salt of the amino group includes a quaternary ammonium group (-NH 4 + , -NR 4 + etc.) salts (e.g., halides, etc.) of the above-mentioned compounds are also included.

[0093] Specific examples of vinyl monomers capable of forming other structural units of the B block include the same monomers as those exemplified as specific examples of monomers capable of forming other structural units of the A block.

[0094] The content of the structural unit represented by (1) in the B block is preferably 5 mass % or less, more preferably 3 mass % or less, and even more preferably 1 mass % or less, and it is particularly preferable that the B block does not contain the structural unit represented by (1).

[0095] When two or more types of structural units are contained in the B block, the various structural units contained in the B block may be contained in the B block in any form such as random copolymerization, block copolymerization, etc., and from the viewpoint of uniformity, it is preferable that they are contained in the B block in the form of random copolymerization. For example, the B block may be formed of a copolymer of structural units consisting of the b1 block and structural units consisting of the b2 block.

[0096] (Block Copolymer) The structure of the block copolymer is preferably a linear block copolymer. The linear block copolymer may have any structure (arrangement), but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, when the A block is represented as A and the B block is represented as B, the structure (arrangement) of the linear block copolymer is preferably (AB) m Type, (AB) m -A type and (BA) m It is preferable that the block copolymer has at least one structure selected from the group consisting of -B type (m is an integer of 1 or more, for example, an integer of 1 to 3). Among these, from the viewpoints of handling during processing and physical properties of the composition, it is preferable that the block copolymer is an AB type diblock copolymer. It is considered that by forming an AB type diblock copolymer, the structural unit represented by formula (1) in the A block and the structural unit represented by formula (3) in the B block are localized, and the block copolymer can efficiently and suitably interact with the pigment and the dispersion medium (solvent). The block copolymer may have other blocks in addition to the A block and the B block.

[0097] The content of the A block is preferably 50% by mass or more, more preferably 55% by mass or more, even more preferably 60% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less, based on 100% by mass of the entire block copolymer. The content of the B block is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, based on 100% by mass of the entire block copolymer. By adjusting the contents of the A block and the B block within the above ranges, the dispersing performance when used as a dispersant is further improved.

[0098] The mass ratio of the A block to the B block in the block copolymer (A block / B block) is preferably 50 / 50 or more, more preferably 55 / 45 or more, and even more preferably 60 / 40 or more, and is preferably 95 / 5 or less, more preferably 90 / 10 or less, and even more preferably 80 / 20 or less. If the mass ratio of the A block to the B block is within the above range, the dispersing performance when used as a dispersant is further improved.

[0099] The content of the structural unit represented by formula (1) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on 100% by mass of the entire block copolymer; and is preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, and particularly preferably 60% by mass or less.

[0100] The content of the structural unit represented by formula (3) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on 100% by mass of the entire block copolymer, and is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0101] The content of the structural unit having a basic group, based on 100% by mass of the entire block copolymer, is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, and is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

[0102] The molecular weight of the block copolymer is measured by gel permeation chromatography (hereinafter referred to as "GPC"). The weight average molecular weight (Mw) of the block copolymer is preferably 3,000 or more, more preferably 5,000 or more, even more preferably 7,000 or more, particularly preferably 10,000 or more, and is preferably 40,000 or less, more preferably 35,000 or less, and even more preferably 30,000 or less. If the weight average molecular weight is within the above range, the dispersion performance when used as a dispersant will be better.

[0103] The molecular weight distribution (PDI) of the block copolymer is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.7 or less. In the present invention, the molecular weight distribution (PDI) is calculated by (weight average molecular weight (Mw) of the block copolymer) / (number average molecular weight (Mn) of the block copolymer). The smaller the PDI, the narrower the molecular weight distribution width, and the copolymer has a uniform molecular weight, and when the PDI value is 1.0, the molecular weight distribution width is the narrowest. In other words, the lower limit of the PDI is 1.0. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.5, it includes those with low molecular weights and those with high molecular weights.

[0104] The amine value of the block copolymer is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and even more preferably 30 mgKOH / g or more, and is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and even more preferably 120 mgKOH / g or less. If the amine value is 10 mgKOH / g or more, the dispersibility of the colorant is further improved, and if it is 200 mgKOH / g or less, the viscosity increase of the coloring composition can be suppressed.

[0105] (Method of Producing Block Copolymer) Examples of methods for producing a block copolymer include a method in which an A block is first produced by a polymerization reaction of a vinyl monomer and then a monomer for a B block is polymerized onto the A block; a method in which a B block is first produced and then a monomer for an A block is polymerized onto the B block; and a method in which the A block and the B block are produced separately and then the A block and the B block are coupled together.

[0106] The polymerization method is not particularly limited, but living radical polymerization is preferred. That is, the block copolymer is preferably one polymerized by living radical polymerization. The living radical polymerization method is preferred in that it maintains the simplicity and versatility of conventional radical polymerization methods, while being less susceptible to termination reactions and chain transfer, and grows without being hindered by side reactions that deactivate the growing end, making it easy to precisely control the molecular weight distribution and produce a polymer with a uniform composition.

[0107] Living radical polymerization methods include, depending on the method of stabilizing the polymer growing end, a method using a transition metal catalyst (ATRP method), a method using a sulfur-based reversible chain transfer agent (RAFT method), a method using an organic tellurium compound (TERP method), etc. Among these methods, the TERP method is preferred from the viewpoints of the variety of monomers that can be used, molecular weight control in the polymer region, uniform composition, and coloring.

[0108] The TERP method is a method in which an organic tellurium compound is used as a chain transfer agent to polymerize a radically polymerizable compound (vinyl monomer), and is a method described, for example, in WO 2004 / 14848, WO 2004 / 14962, WO 2004 / 072126, and WO 2004 / 096870.

[0109] Specific polymerization methods of the TERP method include the following (a) to (d). (a) A method of polymerizing a vinyl monomer using an organotellurium compound represented by formula (6): (b) A method of polymerizing a vinyl monomer using a mixture of an organotellurium compound represented by formula (6) and an azo-based polymerization initiator. (c) A method of polymerizing a vinyl monomer using a mixture of an organotellurium compound represented by formula (6) and an organoditelluride compound represented by formula (7). (d) A method of polymerizing a vinyl monomer using a mixture of an organotellurium compound represented by formula (6), an azo-based polymerization initiator, and an organoditelluride compound represented by formula (7).

[0110] [ka] [In the general formula (6), R 61 R represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group. 62 and R 63 R each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 64 represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amido group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group. In the general formula (7), R 61 represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group.]

[0111] Specific examples of the organic tellurium compound represented by the general formula (6) include ethyl-2-methyl-2-n-butyltellanyl-propionate, ethyl-2-n-butyltellanyl-propionate, (2-hydroxyethyl)-2-methyl-methyltellanyl-propionate, and the organic tellurium compounds described in WO 2004 / 14848, WO 2004 / 14962, WO 2004 / 072126, and WO 2004 / 096870. Specific examples of the organic ditelluride compound represented by the general formula (7) include dimethyl ditelluride, dibutyl ditelluride, and the like. The azo polymerization initiator can be any azo polymerization initiator used in normal radical polymerization without any particular limitation. Examples of the azo polymerization initiator include 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis(1-cyclohexanecarbonitrile) (ACHN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70), and the like.

[0112] In the polymerization step, a vinyl monomer and an organic tellurium compound of general formula (6) are mixed in a vessel purged with an inert gas, and for the purpose of promoting the reaction and controlling the molecular weight and molecular weight distribution depending on the type of vinyl monomer, an azo polymerization initiator and / or an organic ditelluride compound of general formula (7) are further mixed. Examples of the inert gas include nitrogen, argon, and helium. Argon and nitrogen are preferable. The amount of the vinyl monomer used in the above (a), (b), (c), and (d) may be appropriately adjusted depending on the physical properties of the desired copolymer.

[0113] The polymerization reaction can be carried out without a solvent, but may be carried out by stirring the mixture using an aprotic solvent or a protic solvent generally used in radical polymerization. Examples of aprotic solvents that can be used include anisole, benzene, toluene, propylene glycol monomethyl ether acetate, ethyl acetate, and tetrahydrofuran (THF). Examples of protic solvents include water, methanol, and 1-methoxy-2-propanol. The solvent may be used alone or in combination of two or more. The amount of the solvent used may be appropriately adjusted, and is preferably 0.01 ml to 50 ml per 1 g of vinyl monomer. The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the resulting copolymer, but the mixture is usually stirred at 0°C to 150°C for 1 minute to 100 hours. After the polymerization reaction is completed, the solvent used and the remaining vinyl monomer are removed from the resulting reaction mixture by a conventional separation and purification means, and the target copolymer can be separated.

[0114] The growing end of the copolymer obtained by the polymerization reaction is -TeR derived from the tellurium compound. 61 (In the formula, R 61 is the same as above), and is deactivated by handling in air after the polymerization reaction is completed, but tellurium atoms may remain. Since copolymers with tellurium atoms remaining at the terminals are colored and have poor thermal stability, it is preferable to remove the tellurium atoms. Methods for removing tellurium atoms include radical reduction methods, adsorption methods using activated carbon, and adsorption of metals using ion exchange resins, and these methods can also be used in combination. The other end of the copolymer obtained by the polymerization reaction (the end opposite to the growing end) is formed of -CR derived from the tellurium compound. 62 R 63 R 64 (In the formula, R 62 , R 63 and R 64 is R in Eq. (6). 62 , R 63 and R 64 (same as above.)

[0115] (aqueous dispersion medium) Examples of the aqueous dispersion medium include water or an aqueous solvent (a solvent miscible with water). Specifically, examples of the aqueous dispersion medium include alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, 1-methoxy-2-propanol, and 1-butoxy-2-propanol; polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, and glycerin; ethers such as tetrahydrofuran, dioxane, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol, monomethyl ether, and monoethyl ether; ketones such as acetone, methyl ethyl ketone, and isobutyl ketone; and amides such as dimethylformaldehyde and dimethylacetamide. Among these, alcohols and glycols are preferred. The aqueous solvent may be used alone or in combination of two or more.

[0116] The content of the aqueous dispersion medium in the coloring composition is not particularly limited and can be adjusted appropriately.The upper limit of the content of the aqueous dispersion medium in the coloring composition is usually 99% by mass.In addition, the lower limit of the content of the aqueous dispersion medium in the coloring composition is usually 60% by mass, preferably 80% by mass, in consideration of the viscosity suitable for application of the coloring composition.

[0117] Depending on the application, the coloring composition may further contain additives such as a resin for forming a coating film, a surfactant, a leveling agent, a filler, an ultraviolet absorber, an antioxidant, a preservative, an antifungal agent, a viscosity adjuster, a pH adjuster, an antifoaming agent, and a crosslinking agent. In addition, when conductive carbon particles are used in the coloring composition, it can be used for an electrode. In this case, the coloring composition may contain additives such as a resin for forming an electrode, an electrode active material, a surfactant, a film-forming assistant, a leveling agent, a preservative, an antifungal agent, a viscosity adjuster, a pH adjuster, an antifoaming agent, and a crosslinking agent.

[0118] (Resin for coating film formation) The coating film-forming resin is a component that becomes the main body of the film when a coating film is formed using the coloring composition. The coating film-forming resin is not particularly limited, and any resin that has been used in conventional paints can be used. Examples of the coating film-forming resin include thermosetting resins, thermoplastic resins, and polymerizable compounds (polymerizable resins, monomers having one polymerizable unsaturated bond in the molecule, monomers having two or more polymerizable unsaturated bonds in the molecule, oligomers, etc.). The coating film-forming resins can be used alone or in combination of two or more kinds. When the coating film-forming resin is blended in the coloring composition, the content of the coating film-forming resin is preferably 60% by mass to 95% by mass in the total solid content of the coloring composition.

[0119] (thermosetting resin, thermoplastic resin) Examples of thermosetting resins and thermoplastic resins include butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene resins, chlorinated polypropylene resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, vinyl acetate resins, urethane resins, phenolic resins, polyester resins, acrylic resins, alkyd resins, styrene resins, styrene-acrylic resins, polyamide resins, rubber-based resins, cyclized rubbers, epoxy resins, celluloses, polybutadiene, polyimide resins, benzoguanamine resins, melamine resins, urea resins, silicone resins, and fluororesins.

[0120] (polymerizable compound) As the polymerizable resin as the polymerizable compound, a resin in which a crosslinkable group such as a (meth)acrylic compound or cinnamic acid is introduced into a linear polymer having a reactive substituent such as a hydroxy group, a carboxy group, or an amino group via an isocyanate group, an aldehyde group, an epoxy group, etc. is also used. Polymers in which a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth)acrylic compound having a hydroxy group such as a hydroxyalkyl (meth)acrylate are also used.

[0121] (Surfactant) The surfactant may, for example, be a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an amphoteric surfactant. Examples of the nonionic surfactant include a fluorine-based surfactant, a silicone-based surfactant, and a polyoxyethylene-based surfactant. Examples of anionic surfactants include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, higher alcohol sulfate ester salts, aliphatic alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, and special polymer surfactants. Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts. Examples of the amphoteric surfactant include betaine-type compounds, imidazolium salts, imidazolines, and amino acids.

[0122] (Leveling agent) Examples of the leveling agent include silicone-based agents and fluorine-based agents. Examples of the silicone-based agents include dimethyl silicone oil, methylphenyl silicone oil, alkyl-modified silicone, alkoxy-modified silicone, oxyalkyl-modified silicone, glycol-modified silicone, polyether-modified silicone, polyether-modified silicone, and fatty acid ester-modified silicone. Examples of the fluorine-based agents include fluorocarbon compounds and fluorine silicone. These agents can be used alone or in combination of two or more.

[0123] (filling material) Examples of fillers include silicon dioxide, alumina, zinc oxide, potassium titanate fiber, aluminum flakes, stainless steel powder, tin powder, gold powder, metal-plated glass powder, titanic mica, calcium carbonate, barium sulfate, barium carbonate, kaolin, baryta, clay, other metal oxides, and composite metal oxides. These can be used alone or in combination of two or more types to prevent a decrease in viscosity or poor gloss.

[0124] (Resin for forming electrodes) Resins for forming electrodes are used to bond particles of active materials or conductive carbon materials together, or to bond conductive carbon particles to a current collector. Examples of the resins for forming electrodes include acrylic resins, polyurethane resins, polyester resins, phenolic resins, epoxy resins, phenoxy resins, urea resins, melamine resins, alkyd resins, formaldehyde resins, silicone resins, fluororesins, cellulose resins such as carboxymethylcellulose, synthetic rubbers such as styrene butadiene rubber and fluororubber, conductive resins such as polyaniline and polyacetylene, and polymeric compounds containing fluorine atoms such as polyvinylidene fluoride, polyvinyl fluoride, and tetrafluoroethylene. Modified products, mixtures, or copolymers of these resins can also be used. These resins can also be used alone or in combination.

[0125] <Method of producing colored composition> The coloring composition can be prepared by mixing a coloring material, a dispersant (block copolymer), an aqueous dispersion medium, and, if necessary, a resin for forming a coating film and other compounding agents. For mixing, a mixer / disperser such as a paint shaker, a bead mill, a ball mill, a dissolver, or a kneader can be used. The coloring composition is preferably filtered after mixing. Examples of the coloring composition include a coating composition for automobiles.

[0126] The coloring composition can be applied (coated) to a substrate such as a stainless steel plate or an aluminum plate by, for example, roll coating, spin coating, flow coating, slot die coating, spray coating, dip coating, electrostatic coating, electrostatic coating, brush coating, powder coating, or the like. Thereafter, the coating is heated as necessary to evaporate the solvent, and the coating is dried and cured. At this time, heating or irradiation with ultraviolet rays or the like may be performed. The coating obtained by applying the coloring composition may be further coated with one or more layers of a top clear coating to form a top clear coating. The top clear coating is a liquid coating that forms a colorless or colored transparent coating film, which is mainly composed of a resin component and a solvent, and further contains other coating additives as necessary. EXAMPLES

[0127] The present invention will be described in more detail below based on specific examples. The present invention is not limited to the following examples, and can be modified as appropriate within the scope of the present invention. The polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI), amine value, and coating film properties of the block copolymer were evaluated according to the following methods.

[0128] The meanings of the abbreviations are as follows: BTEE: Ethyl 2-methyl-2-n-butyltellanyl-propionate AIBN: 2,2'-azobis(isobutyronitrile) BA: Butyl acrylate M9EGA: polyethylene glycol (degree of polymerization = 9) methyl ether acrylate (NOF Corporation, Blenmer (registered trademark) AME-400) M11EGA: Polyethylene glycol (degree of polymerization = 11) methyl ether acrylate (Green, KOMERATE-A040TT) CHA: Cyclohexyl acrylate IBXA: Isobornyl acrylate DCPA: dicyclopentanyl acrylate DMAEMA: Dimethylaminoethyl methacrylate 4VPy: 4-vinylpyridine PMA: Propylene glycol monomethyl ether acetate MP: 1-methoxy-2-propanol

[0129] (Polymerization rate) Using a nuclear magnetic resonance (NMR) measuring device (Bruker Biospin, model: AVANCE500 (frequency 500 MHz)), 1 H-NMR measurement (solvent: CDCl 3 (Internal standard: TMS) For the obtained NMR spectrum, the integral ratio of the peak derived from the monomer to the peak derived from the polymer was obtained, and the polymerization rate of the monomer was calculated.

[0130] (Weight average molecular weight (Mw) and molecular weight distribution (PDI)) The molecular weight was determined by gel permeation chromatography (GPC) using a high performance liquid chromatograph (Tosoh, model HLC-8320). A column of SHODEX KF-603 (φ6mm×150mm) (SHODEX) was used, and a lithium bromide (10mmol / L)-acetic acid (10mmol / L)-methylpyrrolidone solution was used as the mobile phase, and a differential refractometer was used as the detector. The measurement conditions were: column temperature 40°C, sample concentration 20mg / mL, sample injection volume 10μm, and flow rate 0.2mL / min. A calibration curve was created using polystyrene (molecular weight 70,500, 37,900, 19,920, 10,200, 4,290, 2,630, 1,150) as the standard substance, and the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured. From this measurement, the molecular weight distribution (PDI=Mw / Mn) was calculated.

[0131] (amine value) The amine value represents the mass of potassium hydroxide (KOH) equivalent to the basic component per 1 g of solid content. The measurement sample was dissolved in tetrahydrofuran, and the resulting solution was neutralized with hydrochloric acid (0.1 mol / L)-propanol solution using a potentiometric titrator (product name: GT-06, manufactured by Mitsubishi Chemical Corporation). The inflection point of the titration pH curve was used as the titration end point, and the amine value (B) was calculated using the following formula. B=56.11×Vs×0.1×f / w B: Amine value (mgKOH / g) Vs: Amount of hydrochloric acid (0.1 mol / L)-propanol solution required for titration (mL) f: Potency of hydrochloric acid (0.1 mol / L)-propanol solution w: Mass of the measurement sample (g) (solid content equivalent)

[0132] (Black rating) The black paint was applied to a stainless steel plate using a bar coater (#20) and dried at 60°C for 10 minutes to form a coating, and a test specimen was prepared. The L value of the coating surface of the obtained test piece was measured by removing specular reflection using an L value measuring device (Model CM-2600d, manufactured by Konica Minolta Japan, Inc.) Evaluation was performed on the black paint immediately after preparation and on the black paint after being left at 35°C for 3 weeks after preparation.

[0133] (Microscopic Observation) The black paint was applied to a stainless steel plate using a bar coater (#20) and dried at 60°C for 10 minutes to form a coating, and a test specimen was prepared. The coating surfaces of the obtained test pieces were observed under a microscope, and those where no aggregation was observed were rated as "O", those where slight aggregation was observed were rated as "Δ", and those where aggregation was observed were rated as "X".

[0134] <Synthesis of block copolymer> (Block Copolymer No. 1) In a flask equipped with an argon gas inlet tube and a stirrer, 9.0 g of BA, 18.0 g of M9EGA, ​​0.05 g of AIBN, and 6.8 g of PMA were charged, and after replacing with nitrogen, 0.45 g of BTEE was added and reacted at 60°C for 48 hours to polymerize the A block. The polymerization rate was 100%.

[0135] A mixed solution of 5.0 g of CHA, 7.1 g of DMAEMA, 0.05 g of AIBN, and 3.0 g of PMA, which had been previously purged with argon, was added to the reaction solution, and the mixture was reacted at 60° C. for 55 hours to polymerize block B. The polymerization rate was 93%.

[0136] After the reaction was completed, the reaction solution was poured into stirred n-heptane. The precipitated polymer was filtered by suction and dried to obtain block copolymer No. 1. The obtained block copolymer No. 1 had an Mw of 24,880, a PDI of 1.48, and an amine value of 68 mgKOH / g.

[0137] (Block copolymers No. 2 to 6) Block copolymers No. 2 to 6 were produced in the same manner as in the production of block copolymer No. 1. Table 1 shows the monomers, organotellurium compounds, azo-based polymerization initiators, solvents, reaction conditions, and polymerization rates used. Table 2 shows the composition, Mw, PDI, and amine value of each block copolymer. The content of each structural unit in the copolymer was calculated from the charge ratio and polymerization rate of the monomers used in the polymerization reaction.

[0138] [Table 1]

[0139] [Table 2]

[0140] (Black Paint No. 1~6) Black paints were prepared using the block copolymers No. 1 to 6 obtained above as dispersants. Specifically, each component was added to a 50 mL mayonnaise bottle so as to obtain the composition shown in Table 3, and 66 g of zirconia beads (φ0.3 mm) was added, followed by stirring for 5 hours using a dispersing machine (Owell, SKANDEX DISPERSER BA-S20). After stirring, the beads were filtered off to obtain a pigment dispersion. Black paints No. 1 to 6 were prepared by mixing the obtained pigment dispersion with a clear paint. It was visually confirmed that the carbon black had good dispersibility in the obtained black paints No. 1 to 6.

[0141] [Table 3] Black pigment 1: Trade name "EMPEROR (registered trademark) 2000", manufactured by Cabot Corporation, carbon black, pH 6 to 9 Defoamer: Product name "BYK-024", manufactured by BYK-Chemie, silicone surfactant Acrylic resin: product name "WATERSOL (registered trademark) ACD-2001", manufactured by DIC Corporation, non-volatile content; 40% by mass, solvent; water, propylene glycol-n-butyl ether Melamine resin: product name "Cymel (registered trademark) 303LF", manufactured by Allnex, methylated melamine resin, non-volatile content: 100% by mass

[0142] (Black paint No. 7~9) Pigment dispersions were prepared using the block copolymers No. 2 to 4 obtained above as dispersants. Specifically, each component was added to a 50 mL mayonnaise bottle so as to obtain the composition shown in Table 4, and 66 g of zirconia beads (φ0.3 mm) was added, followed by stirring for 5 hours using a dispersing machine (Owell, SKANDEX DISPERSER BA-S20). After stirring was completed, the beads were filtered off to prepare black paints No. 7 to 9. It was visually confirmed that the dispersibility of carbon nanotubes in the obtained black paints No. 7 to 9 was good.

[0143] [Table 4] Black pigment 2: Product name "Nanocyl 7000", manufactured by NANOCOYL, multi-walled carbon nanotubes Defoamer: Product name "BYK-024", manufactured by BYK-Chemie, silicone surfactant

[0144] Block copolymers No. 1 to 5 have an A block containing a structural unit represented by formula (1) and a B block containing a structural unit represented by formula (3) and a structural unit having a basic group. Black paints No. 1 to 5 containing these block copolymers No. 1 to 5 produced coating films with low L values ​​both immediately after preparation and after storage for 3 weeks. Furthermore, the black paints Nos. 7 to 9 prepared using block copolymers Nos. 2 to 4 also had excellent dispersion performance for carbon nanotubes (carbon particles). Since block copolymer No. 1 has a similar structure to block copolymer No. 2, it is considered that block copolymer No. 1 also has high dispersion performance for carbon nanotubes (carbon particles).

[0145] Block copolymer No. 6 does not have a B block containing a structural unit represented by formula (3). The black paint using this block copolymer No. 6 had a high L value for the coating film both immediately after preparation and after storage for three weeks. [Industrial Applicability]

[0146] The colored composition of the present invention is useful for automobile paints and the like because it forms a coating film with high jet black color.

Claims

1. Contains a black colorant, a dispersant, and an aqueous dispersion medium, The coloring composition, characterized in that the dispersant contains a block copolymer having an A block containing a structural unit represented by formula (1) and a B block containing a structural unit represented by formula (3) and a structural unit having a basic group. 【Chemistry 1】 [In formula (1), n1 represents an integer of 2 to 30. 11 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 12 represents an alkylene group having 1 to 3 carbon atoms. 13 represents a hydrogen atom or a methyl group. 12 may be the same or different. 【Chemistry 2】 [In formula (3), R 31 represents an alicyclic hydrocarbon group. ３ represents O or NH. 32 represents a hydrogen atom or a methyl group.

2. The colored composition according to claim 1, wherein the content of the structural unit represented by the formula (1) is 20% by mass to 95% by mass in 100% by mass of the A block.

3. 3. The colored composition according to claim 1, wherein the content of the structural unit represented by the formula (3) is 15% by mass to 80% by mass in 100% by mass of the B block.

4. The coloring composition according to any one of claims 1 to 3, wherein in the B block, a mass ratio of the structural unit represented by formula (3) to the structural unit having a basic group (structural unit represented by formula (3) / structural unit having a basic group) is 0.15 to 4.

0.

5. The colored composition according to any one of claims 1 to 4, wherein the A block further contains a structural unit represented by formula (2). 【Chemistry 3】 [In formula (2), R 21 R represents a chain hydrocarbon group which may have a substituent. 22 represents a hydrogen atom or a methyl group.

6. The colored composition according to any one of claims 1 to 5, wherein the block copolymer has an amine value of 10 mg KOH / g to 200 mg KOH / g.

7. The colored composition according to any one of claims 1 to 6, wherein the structural unit having a basic group is a structural unit represented by formula (4): 【Chemistry 4】 [In formula (4), R 41 and R 42 R each independently represents a chain or cyclic hydrocarbon group which may have a substituent. 41 and R 42 may be bonded to each other to form a cyclic structure. 43 represents a divalent hydrocarbon group. 4 represents O or NH. 44 represents a hydrogen atom or a methyl group.

8. The colored composition according to any one of claims 1 to 7, wherein a mass ratio of the A block to the B block (A block / B block) in the block copolymer is from 50 / 50 to 95 / 5.

9. The colored composition according to any one of claims 1 to 8, wherein the molecular weight distribution (PDI) of the block copolymer is 2.5 or less.

10. The colored composition according to any one of claims 1 to 9, wherein the block copolymer has a weight average molecular weight (Mw) of 3,000 to 40,000.

11. The colored composition according to any one of claims 1 to 10, wherein the block copolymer is polymerized by living radical polymerization.

12. The colored composition according to claim 11, further comprising a coating film-forming resin.

13. The colored composition according to claim 12, which is an automotive coating composition.

14. A coating film formed from the colored composition according to any one of claims 1 to 13.

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