Coloring composition and coating film

Abstract

To provide a coloring composition that can improve the transparency and chroma of a coating layer.SOLUTION: A coloring composition contains a blue coloring material, a dispersant, and an aqueous dispersion medium. The dispersant contains a block copolymer that has an A block having a unit of formula (1) and a B block containing a unit of formula (3) and a unit having a basic group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a coloring composition containing a blue coloring agent, a dispersant, and an aqueous dispersion medium.

Background Art

[0002] In recent years, from the viewpoint of preventing air pollution, it has been required to reduce the emission amount of volatile organic compounds (VOCs) from factories and workplaces. Therefore, for the paint used for coating metal plates constituting the body of an automobile or the like, a switch to an aqueous paint is being considered. In addition, in automotive paints, not only coating film properties such as high durability, acid resistance, car wash scratch resistance, and chipping resistance are required, but also the finish appearance of the coating film such as transparency and color development is required more than ever.

[0003] The coloring agent used in the paint generally has a hydrophobic surface. In addition, the dispersant used in the solvent-based colored paint has low solubility in water and is inferior in dispersion stability in the aqueous dispersion medium. In particular, carbon particles such as carbon black used as a black coloring agent have a small primary particle diameter and a very large specific surface area, so the cohesive force is very strong. Therefore, it is difficult to uniformly disperse the carbon particles in the aqueous dispersion medium, and there is a problem that they aggregate even if they are dispersed.

[0004] Therefore, in the paint using carbon black as a black coloring agent, a technique for improving the dispersibility of carbon black has been proposed. For example, Patent Document 1 describes a highly jet-black carbon black dispersion in which carbon black having a DBP absorption of 150 ml / 100 g or less, an average primary particle diameter of 15 nm or less, a specific surface area of 500 m 2 / g or less, and a pH in the acidic to neutral region is finely dispersed in an aqueous medium by a dispersant (in some cases, jet-blackness when the coloring agent is a black coloring agent among color developments). In this Patent Document 1, the dispersibility of carbon black is improved by controlling the physical properties of carbon black (see Patent Document 1 (Claim 1, Paragraphs 0019, 0021, 0024)).

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

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] In aqueous paints using carbon particles as a black coloring material, paints with improved dispersibility of carbon particles have been proposed. By the way, since carbon black is a reddish-black color, a blue coloring material (blueing agent) such as a phthalocyanine pigment may be added to enhance the jet-blackness. However, in aqueous paints, there has been room for improvement in the dispersibility of blue coloring materials (especially phthalocyanine pigments). The present invention has been made in view of the above circumstances, and an object thereof is to provide an aqueous coloring composition containing a blue coloring material, which can improve the transparency and chroma of a coating film when applied.

Means for Solving the Problems

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

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

[0010] [Chemical formula] [In formula (3), R 31 represents an aromatic group which may have a substituent. n3 represents 0 or 1. Z 3 represents O or NH. R 32 represents a hydrogen atom or a methyl group.]

[0011] The block copolymer contained in the coloring composition of the present invention as a dispersant has a high affinity with the aqueous dispersion medium for the structural unit represented by formula (1) contained in the A block, and the structural unit represented by formula (3) and the structural unit having a basic group contained in the B block are adsorbed on the blue colorant. Therefore, the coloring composition of the present invention has high dispersibility of the blue colorant and can form a coating film with excellent transparency and chroma. [Advantages of the Invention]

[0012] The aqueous coloring composition containing the blue colorant (particularly phthalocyanine-based pigment) of the present invention can obtain a coating film with excellent transparency and chroma. In addition, since the dispersant used in the coloring composition of the present invention can improve the jet blackness of the coating film even when used for a black colorant, the coloring composition of the present invention can also be used as a bluing agent for a black coloring composition. [Embodiments for Carrying Out the Invention]

[0013] <Coloring Composition> The coloring composition of the present invention contains a dispersant (block copolymer), a blue coloring agent, and an aqueous dispersion medium.

[0014] (Blue Coloring Agent) The blue coloring agent used in the present invention is not particularly limited, and pigments and dyes used as blue coloring agents for conventional paints can be used. A blue pigment is preferable from the viewpoints of light resistance and heat resistance. Examples of the blue pigment include organic pigments mainly composed of organic compounds such as phthalocyanine-based pigments, anthraquinone-based pigments, and dioxazine-based pigments, and one or more of these can be mixed and used. Among these, phthalocyanine-based pigments are preferable, and metal phthalocyanine pigments and monohalogenated metal phthalocyanine pigments (halogenated metal phthalocyanine pigments having one halogen atom in the molecule) are more preferable. Note that since polyhalogenated metal phthalocyanine pigments (halogenated metal phthalocyanine pigments having two or more halogen atoms in the molecule) are green pigments, the phthalocyanine-based pigments used as blue pigments do not include polyhalogenated metal phthalocyanine pigments.

[0015] As the phthalocyanine-based pigment, the compound represented by the general formula (8) is particularly preferable. Copper phthalocyanine pigments and monohalogenated copper phthalocyanine pigments have a transmission region in the short wavelength region, so a coloring layer with higher luminance can be formed.

[0016] [Chemical Formula] [In formula (8), R 8 each independently represents a hydrogen atom or a halogen atom. However, the number of halogen atoms in R 8 is 0 or 1.]

[0017] R 8 is preferably all hydrogen atoms from the viewpoint of transmitting light well in the short wavelength region and easily obtaining the effects of the present invention.

[0018] According to the compounds classified as pigments in the Color Index (C.I.) as cyan pigments, specifically, C.I. 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, etc. can be mentioned. As phthalocyanine-based pigments, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 17:1, 75 are preferable, and as copper phthalocyanine pigments and monohalogenated copper phthalocyanine pigments, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 17:1 are preferable. As anthraquinone-based pigments, C.I. Pigment Blue 60 is preferable. As dioxazine-based pigments, C.I. Pigment Blue 80 is preferable.

[0019] In order to obtain jet blackness, the coloring composition of the present invention may use the above cyan coloring material and black coloring material in combination. In that case, the mass ratio of the cyan coloring material / black coloring material is preferably 80 / 20 to 5 / 95.

[0020] The black coloring material is not particularly limited, and pigments and dyes used as black coloring materials for conventional paints can be used. From the viewpoints of light resistance and heat resistance, black pigments are preferable. Examples of black pigments include carbon blacks such as furnace black, channel black, acetylene black, thermal black, lamp black, bone black; carbon nanotubes; carbon nanofibers; fullerenes; graphite; graphene; perylene-based pigments; lactam-based pigments; titanium black; metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver; composite oxides; metal sulfides; metal sulfates; metal carbonates, etc. Preferably, it is at least one carbon particle selected from the group consisting of carbon black and carbon nanotubes.

[0021] As long as the preferable physical properties of the present invention are not impaired, other colorants than blue and black colorants may be contained for adjusting the hue or the like.

[0022] The other colorants are not particularly limited, and pigments and dyes used as colorants for conventional paints can be used, and pigments are preferable from the viewpoints of light resistance and heat resistance. The pigment may be either an organic pigment or an inorganic pigment, but an organic pigment mainly composed of an organic compound is preferable.

[0023] Examples of the organic pigment include pigments of various colors such as red pigments, yellow pigments, green pigments, purple pigments, and orange pigments. The structure of the organic pigment includes azo pigments such as phthalocyanine-based pigments, monoazo-based pigments, diazo-based pigments, and condensed diazo-based pigments, diketopyrrolopyrrole-based pigments, isoindolinone-based pigments, isoindoline-based pigments, quinacridone-based pigments, indigo-based pigments, thioindigo-based pigments, quinophthalone-based pigments, dioxazine-based pigments, anthraquinone-based pigments, perylene-based pigments, and perinone-based pigments.

[0024] The other colorants contained in the coloring composition may be only one kind or a plurality of kinds.

[0025] Examples of red pigments include C.I.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, 237, 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.

[0026] Examples of yellow pigments include C.I.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, etc.

[0027] Examples of green pigments include C.I.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, diphenoxyphosphinyl oxyaluminum phthalocyanine, diphenylphosphinyl oxyaluminum phthalocyanine, polyhalogenated diphenoxyphosphinyl oxyaluminum phthalocyanine, polyhalogenated diphenylphosphinyl oxyaluminum phthalocyanine, etc.

[0028] Examples of purple pigments include C.I.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, 50, etc.

[0029] Examples of orange pigments include C.I.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, 79, etc.

[0030] Examples of inorganic pigments include barium sulfate, lead sulfate, titanium oxide (rutile type, anatase type, etc.), lead yellow, red iron oxide, chromium oxide, etc.

[0031] The number average particle diameter of the pigment may be appropriately selected according to its use and is not particularly limited. 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.

[0032] The pigment may contain a dye derivative as a dispersion aid. As the dye derivative, it is preferable to contain an acidic dye derivative having an acidic group in order to adsorb by ionic bonding with a basic group (for example, an amino group) in the block copolymer contained in the dispersant. This dye derivative is one in which an acidic group is introduced into the dye skeleton. As the dye skeleton, a skeleton identical or similar to the pigment constituting the coloring composition, or a skeleton identical or similar to the compound serving as the raw material of the pigment is preferable. 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, a perylene-based dye skeleton, etc., and preferably a phthalocyanine-based dye skeleton. As the acidic group introduced into the dye skeleton, a carboxy group, a phosphoric acid group, and a sulfonic acid group are preferable. In view of the convenience of synthesis and the strength of acidity, a sulfonic acid group is preferable. Further, 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.

[0033] The amount of the dye derivative used is not particularly limited, but for example, it is preferably 4 parts by mass to 17 parts by mass with respect to 100 parts by mass of the pigment.

[0034] From the perspective of luminance, the upper limit of the content of the colorant 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. Further, the lower limit of the content of the colorant in the coloring composition is usually 3% 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 components other than the dispersion medium described later.

[0035] The content of the dispersant with respect to the colorant in the coloring composition is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and preferably 200 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 80 parts by mass or less with respect to 100 parts by mass of the colorant.

[0036] (Dispersant) The dispersant used in the present invention contains a block copolymer having an A block containing a structural unit represented by the formula (1) and a B block containing a structural unit represented by the 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 75% by mass or more of the block copolymer, and more preferably is composed only of the block copolymer. It is considered that, for example, the aromatic group in the structure (B block) of the block copolymer strongly binds to the aromatic group derived from the colorant, and the B block adsorbs to the blue colorant, thereby exerting an action of enhancing the dispersibility of the blue colorant.

[0037] The dispersant can facilitate the dispersion of the coloring material by being prepared as a dispersant solution before preparing the coloring composition. As the solvent used in the dispersant solution, a solvent that can dissolve the dispersant, does not react with these components, and has appropriate volatility is preferable. Examples of the solvent include the 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 adjusted as appropriate. The upper limit value of the content of the solvent in the dispersant solution is usually 99% by mass. Also, considering the viscosity suitable for the production of the coloring composition described later, the lower limit value of the content of the dispersion medium in the dispersant solution is usually 10% by mass, and preferably 30% by mass.

[0038] (Block copolymer) In the present invention, "A block" can be rephrased as "A segment", and "B block" can be rephrased as "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 the vinyl monomer has polymerized to become a carbon-carbon single bond. "(Meth)acryl" 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".

[0039] (A block) The A block is a block containing a structural unit represented by formula (1). The structural unit represented by formula (1) in the A block may be only one kind or may have two or more kinds.

[0040] [Chemical formula] [In formula (1), n1 represents an integer of 2 to 30. R 11 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 12represents an alkylene group having 1 to 3 carbon atoms. R 13 represents a hydrogen atom or a methyl group. Note that a plurality of R 12 may be the same or different from each other.]

[0041] n1 in formula (1) is 2 or more, preferably 5 or more, more preferably 10 or more and 30 or less, preferably 20 or less, more preferably 15 or less.

[0042] R 11 The alkyl group having 1 to 3 carbon atoms represented by may be linear or branched, but a linear one is preferred. The above R 11 Specific examples of the alkyl group having 1 to 3 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

[0043] R 12 The alkylene group having 1 to 3 carbon atoms represented by may be linear or branched, but a linear one is preferred. Specific examples of the alkylene group having 1 to 3 carbon atoms represented by the above R 12 include a methylene group, an ethylene group, a trimethylene group, and a propane-1,2-diyl group. R 12 is preferably an ethylene group or a trimethylene group.

[0044] Examples of the monomer constituting the structural unit represented by formula (1) include (meth)acrylates having a polyalkylene glycol structure. The polyalkylene glycol moiety may be, for example, a mixture of ethylene oxide and propylene oxide. Examples of the (meth)acrylate having a polyalkylene glycol structure include (meth)acrylates having a polyethylene glycol structure such as polyethylene glycol (degree of polymerization = 2 to 30) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization = 2 to 30) ethyl ether (meth)acrylate, and polyethylene glycol (degree of polymerization = 2 to 30) propyl ether (meth)acrylate; and (meth)acrylates having a polypropylene glycol structure such as polypropylene glycol (degree of polymerization = 2 to 30) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization = 2 to 30) ethyl ether (meth)acrylate, and polypropylene glycol (degree of polymerization = 2 to 30) propyl ether (meth)acrylate.

[0045] The content of the structural unit represented by formula (1) is preferably 20% by mass or more, more preferably 35% by mass or more, still more preferably 50% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 80% by mass or less in 100% by mass of the A block. When the content is 20% by mass or more, the affinity with the aqueous dispersion medium is further improved, and when it is 95% by mass or less, the affinity with the resin for film formation becomes better.

[0046] The A block preferably further contains a structural unit represented by formula (2). The structural unit represented by formula (2) in the A block may be only one kind or may have two or more kinds. When the A block has the structural unit represented by formula (2), the affinity with the resin for film formation is further improved.

[0047]

Chemical formula

[0048] R 21 Examples of the linear hydrocarbon group represented by R 21 include a linear alkyl group, a branched alkyl group, etc. The number of carbon atoms of the linear alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-lauryl group, etc. The number of carbon atoms of the branched alkyl group is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a neopentyl group, an isooctyl group, etc.

[0049] R 21 Examples of the substituent which the linear hydrocarbon group represented by R 21 has include a halogen group, an alkoxy group, a benzoyl group (-COC6H5), a hydroxy group, etc.

[0050] R 21 Examples of the alicyclic hydrocarbon group represented by R 21 include a cyclic alkyl group having a monocyclic structure, an alkyl group having a polycyclic structure, etc., and each may have a chain portion. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 4 to 18, more preferably 6 to 12, and even more preferably 6 to 10. Examples of the cyclic alkyl group having a monocyclic structure include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl 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.

[0051] R 21Examples of the substituent of the alicyclic hydrocarbon group represented by include a halogen group, an alkoxy group, a chain alkyl group, a hydroxy group, and the like.

[0052] Examples of the vinyl monomer that forms the structural unit represented by formula (2) include (meth)acrylates having a chain alkyl group (linear alkyl group or branched alkyl group), (meth)acrylates having an alicyclic alkyl group, and the like. Among these, (meth)acrylates having a chain alkyl group (linear alkyl group or branched alkyl group) are preferred.

[0053] 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, n-stearyl (meth)acrylate, and the like.

[0054] 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.

[0055] 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.

[0056] Examples of the polycyclic structure include cyclic alkyl groups having a bridged ring structure (e.g., adamantyl group, norbornyl group, isobornyl group). Specific examples of the (meth)acrylate having a polycyclic structure include isobornyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, dicyclopentanyl oxyethyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and the like.

[0057] When containing the structural unit represented by formula (2), the content is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 65% by mass or less, still 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 resin for film formation is further improved, and if it is 80% by mass or less, the affinity with the aqueous dispersion medium is better.

[0058] The A block may be only the structural unit represented by formula (1), or 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, still more preferably 90% by mass or more.

[0059] Specific examples of the vinyl monomer capable of forming other structural units of the A block include (meth)acrylate having a hydroxy group, (meth)acrylate having a lactone-modified hydroxy group, (meth)acrylate having an alkoxy group, (meth)acrylate having an acidic group, (meth)acrylic acid, (meth)acrylate having a cyclic ether group, and the like.

[0060] Examples of the (meth)acrylate 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, and the like. Among these, (meth)acrylate having a hydroxyalkyl group with 1 to 5 carbon atoms is more preferable.

[0061] Examples of the (meth)acrylate having a lactone-modified hydroxy group include those obtained by adding lactone to the (meth)acrylate having a hydroxy group, and those obtained by adding caprolactone are preferable. The addition amount of caprolactone is preferably 1 mol to 20 mol, more preferably 1 mol to 10 mol. Examples of the (meth)acrylate having a lactone-modified hydroxy group include a 1-mol adduct of caprolactone to 2-hydroxyethyl (meth)acrylate, a 2-mol adduct of caprolactone to 2-hydroxyethyl (meth)acrylate, a 3-mol adduct of caprolactone to 2-hydroxyethyl (meth)acrylate, a 4-mol adduct of caprolactone to 2-hydroxyethyl (meth)acrylate, a 5-mol adduct of caprolactone to 2-hydroxyethyl (meth)acrylate, a 10-mol adduct of caprolactone to 2-hydroxyethyl (meth)acrylate, and the like.

[0062] Examples of the (meth)acrylate having an alkoxy group include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and the like.

[0063] Examples of the acidic group include a carboxy group (-COOH), a sulfonic acid group (-SO3H), a phosphoric acid group (-OPO3H2), a phosphonic acid group (-PO3H2), and a phosphinic acid group (-PO2H2). Examples of the (meth)acrylate having the 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.

[0064] Examples of the (meth)acrylate having a carboxy group include monomers obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride, or phthalic anhydride with a (meth)acrylate having a hydroxy group such as carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, or 2-(meth)acryloyloxyethyl phthalate. Examples of the (meth)acrylate having a phosphoric acid group include 2-(phosphonooxy)ethyl (meth)acrylate. Examples of the (meth)acrylate having a sulfonic acid group include ethyl sulfonate (meth)acrylate.

[0065] Examples of the (meth)acrylate 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.

[0066] The A block preferably contains substantially no structural unit represented by formula (3) below, structural unit having a basic group, and structural unit having a basic group forming a salt. That is, the content rates of the structural unit represented by (3), the structural unit having a basic group, and the structural unit having a basic group forming a salt are preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, and particularly preferably not containing the structural unit represented by (3), the structural unit having a basic group, and the structural unit having a basic group forming a salt, in 100% by mass of the A block.

[0067] 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 any mode such as random copolymerization or block copolymerization in the A block, and are preferably contained in the mode of random copolymerization from the viewpoint of uniformity. For example, the A block may be formed of a copolymer of a structural unit composed of an a1 block and a structural unit composed of an a2 block.

[0068] (B block) The B block is a block containing a structural unit represented by formula (3) and a structural unit having a basic group.

[0069] (Structural unit represented by formula (3)) The structural unit represented by formula (3) in the B block may be only one type or may have two or more types.

[0070] [In Chemical Formula] [In formula (3), R 31 represents an aromatic group which may have a substituent. n3 represents 0 or 1. Z 3 represents O or NH. R 32 represents a hydrogen atom or a methyl group.]

[0071] R 31Examples of the aromatic group represented by [the formula] include aryl groups. The number of carbon atoms in the aromatic group is preferably 6 to 12, more preferably 6 to 8. Specific examples of the aromatic group include a phenyl group and a naphthyl group.

[0072] R 31 Examples of the substituent of the aromatic group represented by [the formula] include a halogen group, an alkyl group, an alkoxy group, a hydroxy group, and the like.

[0073] The structural unit represented by the formula (3) is preferably the structural unit represented by the formula (31) or the structural unit represented by the formula (32).

[0074] [Chemical formula] [In the formulas (31) and (32), R 32 represents a hydrogen atom or a methyl group. n3 represents 0 or 1. R 33 to R 37 are the same or different and represent a hydrogen atom, a halogen group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a hydroxy group.]

[0075] Specific examples of the vinyl monomer forming the structural unit represented by the formula (3) include benzyl (meth) acrylate, phenyl (meth) acrylate, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, etc., and preferably benzyl (meth) acrylate and N-benzyl (meth) acrylamide.

[0076] The content of the structural unit represented by the formula (3) is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less, still 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 dispersion performance with respect to 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.

[0077] (Structural unit having a basic group) As the structural unit having a basic group, any structural unit derived from a vinyl monomer having a basic group may be used. As the basic group, an amino group is preferably used from the viewpoint of easy availability of raw materials and ease of synthesis. The amino group in the present specification includes, in addition to the structure of a general amino group (-NH2), -NHR in which H is substituted with a hydrocarbon group 41 , -NR 41 R 42 (R 41 , R 42 each independently represents a linear or cyclic hydrocarbon group. Further, R 41 and R 42 may be bonded to each other to form a cyclic structure.), a substituted amino group represented by, and a nitrogen-containing heterocyclic group (such as a pyridyl group and an imidazole group).

[0078] The structural unit having a basic group is preferably a structural unit represented by the formula (4) or a structural unit represented by the formula (5). The structural unit represented by the formula (4) or the structural unit represented by the formula (5) in the B block may be only one kind or may have two or more kinds.

[0079] [Chemical formula] [In the formula (4), R 41 and R 42 each independently represents a linear or cyclic hydrocarbon group which may have a substituent. R 41 and R 42 may be bonded to each other to form a cyclic structure. R 43 represents a divalent hydrocarbon group. Z 4 represents O or NH. R 44 represents a hydrogen atom or a methyl group.]

[0080] R 41 and R 42Examples of the chain hydrocarbon group represented by [chain hydrocarbon group] include linear alkyl groups, branched alkyl groups, etc. The number of carbon atoms in the linear alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. Examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, etc. The number of carbon atoms in the branched alkyl group is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5. Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, neopentyl group, isooctyl group, etc.

[0081] R 41 and R 42 Examples of the substituent of the chain hydrocarbon group represented by [chain hydrocarbon group] include halogen group, alkoxy group, benzoyl group (-COC6H5), hydroxy group, etc.

[0082] R 41 and R 42 Examples of the cyclic hydrocarbon group represented by [cyclic hydrocarbon group] include cyclic alkyl groups, aromatic groups, etc., and the cyclic alkyl group and the aromatic group may have a chain portion. The number of carbon atoms in 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 cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc. The number of carbon atoms in 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 phenyl group, tolyl group, xylyl group, mesityl group, etc. Examples of the chain portion of the cyclic alkyl group having a chain portion and 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.

[0083] R 41 and R42 Examples of the substituent of the cyclic hydrocarbon group represented by include a halogen group, an alkoxy group, a linear alkyl group, a hydroxy group, and the like.

[0084] R 41 or R 42 Examples of the cyclic structure formed by bonding with each other include, for example, a nitrogen-containing heterocyclic ring having 5 to 7 members or a condensed ring formed by condensing two of these. The nitrogen-containing heterocyclic ring preferably has no aromaticity, and a saturated ring is more preferable. Specifically, the structures represented by the following formulas (4-1), (4-2), and (4-3) can be mentioned.

[0085] [Chemical formula] [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, a plurality of existing R 45 may be the same or different from each other.]

[0086] R 43 Examples of the divalent hydrocarbon group represented by include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, an arenediyl group having 6 to 10 carbon atoms, and the like. Among these, an alkylene group having 1 to 10 carbon atoms is preferable. The alkylene group may be linear or branched, but a linear one is preferable. The number of carbon atoms of 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, a heptamethylene group, and the like.

[0087] Specific examples of the vinyl monomer that forms the structural unit represented by the formula (4) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, ethylaminoethyl (meth)acrylate, ethylaminopropyl (meth)acrylate, ethylaminobutyl (meth)acrylate, propylaminoethyl (meth)acrylate, propylaminopropyl (meth)acrylate, propylaminobutyl (meth)acrylate, dimethylaminopropyl (meth)acrylamide, and the like.

[0088] [Chemical formula] [In formula (5), R 81 , R 82 and R 83 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. R 84 represents a nitrogen-containing heterocyclic group. m8 represents an integer of 0 to 4.]

[0089] R 81 ~R 83 The number of carbon atoms of the alkyl group in is preferably 1 to 6, more preferably 1 to 4. As the alkyl group, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable. R 81 ~R 83 The substituent in is not particularly limited, and examples thereof include a carboxy group, a sulfonic acid group, esters and salts thereof; an amino group; a hydroxy group and the like. R 81 ~R 83 is preferably a hydrogen atom.

[0090] R 84 Examples of the nitrogen-containing heterocyclic group represented by include a 4-pyridyl group, a 1-imidazole group, a 2-pyridyl group, a 9-carbazole group, etc., and a 4-pyridyl group is preferable.

[0091] m8 is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and still more preferably 0.

[0092] Examples of the vinyl monomer that forms 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-vinylpyridine, 9-vinylcarbazole, and the like. Among these, 4-vinylpyridine is preferred.

[0093] The content of the structural unit having a basic group is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less, still 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 dispersion performance with respect to the coloring material is further improved, and if it is 85% by mass or less, an increase in the viscosity of the coloring composition can be suppressed.

[0094] In the B block, the 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 preferably 0.15 or more, more preferably 0.2 or more, still more preferably 0.4 or more, and preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less.

[0095] 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, still more preferably 90% by mass or more in 100% by mass of the B block. The B block may be composed only of the structural unit represented by formula (3) and the structural unit having a basic group.

[0096] The structural unit having a basic group may have a part of the basic group forming a salt. Examples of the salt of the basic group include inorganic salts such as halide salts (F, Cl, Br, I, etc.) and sulfates of the basic group; sulfonates, sulfates, phosphates or carboxylates of organic compounds. In addition, as the salt of the basic group, it is preferably a salt of an amino group from the viewpoint of easy availability of raw materials and synthesis. In this specification, as the salt of the amino group, salts of quaternary ammonium groups (-NH4 + , -NR4 + , etc.) (for example, halides, etc.) are also included.

[0097] Specific examples of the vinyl monomer capable of forming other structural units of the B block can be the same as those exemplified as specific examples of the monomer capable of forming other structural units of the A block.

[0098] The content of the structural unit represented by (1) in the B block is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less, and it is particularly preferable not to contain the structural unit represented by (1).

[0099] When two or more structural units are contained in the B block, the various structural units contained in the B block may be contained in any mode such as random copolymerization or block copolymerization in the B block, and it is preferably contained in the mode of random copolymerization from the viewpoint of uniformity. For example, the B block may be formed of a copolymer of a structural unit composed of a b1 block and a structural unit composed of a b2 block.

[0100] (Block copolymer) The structure of the block copolymer is preferably a linear block copolymer. Also, the linear block copolymer may have any structure (sequence), 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, (A-B) m type, (A-B) m -A type and (B-A) mIt is preferably a copolymer having at least one structure selected from the group consisting of type - B (where m is an integer of 1 or more, for example, an integer from 1 to 3). Among these, from the viewpoints of handling properties during processing and physical properties of the composition, an A - B type diblock copolymer is preferred. By constituting an A - B type diblock copolymer, the structural unit represented by formula (1) is localized in the A block and the structural unit represented by formula (3) is localized in the B block, and it is considered that they can preferably act on the pigment and the dispersion medium (solvent) efficiently. The block copolymer may have other blocks in addition to the A block and the B block.

[0101] The content of the A block is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less in 100% by mass of the whole block copolymer. The content of the B block is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less in 100% by mass of the whole block copolymer. By adjusting the contents of the A block and the B block within the above ranges, the dispersion performance when used as a dispersant is further improved.

[0102] 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, still more preferably 60 / 40 or more, and preferably 95 / 5 or less, more preferably 90 / 10 or less, still more preferably 80 / 20 or less. If the mass ratio of the A block to the B block is within the above range, the dispersion performance when used as a dispersant is further improved.

[0103] The content rate of the structural unit represented by formula (1) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, particularly preferably 60% by mass or less in 100% by mass of the entire block copolymer.

[0104] The content rate of the structural unit represented by formula (3) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less in 100% by mass of the entire block copolymer.

[0105] The content rate of the structural unit having a basic group is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less in 100% by mass of the entire block copolymer.

[0106] 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, still more preferably 7,000 or more, particularly preferably 10,000 or more, and preferably 40,000 or less, more preferably 35,000 or less, still more preferably 30,000 or less. When the weight average molecular weight is within the above range, the dispersion performance when used as a dispersant becomes better.

[0107] 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 determined by (weight average molecular weight (Mw) of the block copolymer) / (number average molecular weight (Mn) of the block copolymer). The smaller the PDI, the narrower the molecular weight distribution, and the copolymer has a more uniform molecular weight. When the value is 1.0, the molecular weight distribution is the narrowest. That is, the lower limit value of PDI is 1.0. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.5, it will contain components with a small molecular weight or a large molecular weight.

[0108] 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 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 dispersion performance with respect to the coloring material is further improved, and if it is 200 mgKOH / g or less, an increase in the viscosity of the coloring composition can be suppressed.

[0109] (Method for producing block copolymer) Examples of the method for producing the block copolymer include a method in which the A block is first produced by a polymerization reaction of a vinyl monomer and then the monomer of the B block is polymerized to the A block; a method in which the B block is first produced and then the monomer of the A block is polymerized to the B block; and a method in which the A block and the B block are separately produced and then the A block and the B block are coupled.

[0110] The polymerization method is not particularly limited, but living radical polymerization is preferred. That is, as the block copolymer, those polymerized by living radical polymerization are preferred. The living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method, and is less likely to cause termination reactions and chain transfer, and grows without being hindered by side reactions that deactivate the growing ends. Therefore, it is preferred in terms of precise control of the molecular weight distribution and easy production of polymers with a uniform composition.

[0111] In living radical polymerization methods, depending on the method of stabilizing the polymerization growth terminus, there are methods such as using a transition metal catalyst (ATRP method); using a sulfur-based reversible chain transfer agent (RAFT method); using an organic tellurium compound (TERP method). Among these methods, from the viewpoints of the diversity of monomers that can be used, molecular weight control in the polymer region, uniform composition, or coloring, it is preferable to use the TERP method.

[0112] The TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent, and is, for example, the method described in International Publication No. 2004 / 14848, International Publication No. 2004 / 14962, International Publication No. 2004 / 072126, and International Publication No. 2004 / 096870.

[0113] Specific polymerization methods of the TERP method include the following (a) to (d). (a) A method of polymerizing a vinyl monomer using an organic tellurium compound represented by the formula (6). (b) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the formula (6) and an azo-based polymerization initiator. (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 compound represented by the formula (7). (d) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the formula (6), an azo-based polymerization initiator, and an organic ditelluride compound represented by the formula (7).

[0114]

Chemical formula

[0115] Specific examples of the organic tellurium compound represented by General Formula (6) include ethyl-2-methyl-2-n-butyltellanyl-propionate, ethyl-2-n-butyltellanyl-propionate, (2-hydroxyethyl)-2-methyl-methyltellanyl-propionate, etc., and the organic tellurium compounds described in International Publication No. 2004 / 14848, International Publication No. 2004 / 14962, International Publication No. 2004 / 072126, and International Publication No. 2004 / 096870. Specific examples of the organic ditelluride compound represented by General Formula (7) include dimethylditelluride, dibutylditelluride, etc. The azo-based polymerization initiator can be used without particular limitation as long as it is an azo-based polymerization initiator used in ordinary radical polymerization. For example, 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), etc. can be mentioned.

[0116] In the polymerization step, in a container substituted with an inert gas, a vinyl monomer, the organic tellurium compound of General Formula (6), and, depending on the type of the vinyl monomer, for the purposes of promoting the reaction, controlling the molecular weight and molecular weight distribution, etc., an azo-based polymerization initiator and / or the organic ditelluride compound of General Formula (7) are further mixed. At this time, examples of the inert gas include nitrogen, argon, helium, etc. Preferably, argon and nitrogen are good. The amount of the vinyl monomer used in the above (a), (b), (c) and (d) may be appropriately adjusted according to the physical properties of the target copolymer.

[0117] The coincidence reaction can be carried out without a solvent, but it may also be carried out by using an aprotic solvent or a protic solvent commonly used in radical polymerization and stirring the mixture. Examples of aprotic solvents that can be used include anisole, benzene, toluene, propylene glycol monomethyl ether acetate, ethyl acetate, tetrahydrofuran (THF), etc. Examples of protic solvents include water, methanol, 1-methoxy-2-propanol, etc. The solvent may be used alone or in combination of two or more. The amount of the solvent used may be adjusted as appropriate. For example, 0.01 ml to 50 ml is preferable with respect to 1 g of the vinyl monomer. The reaction temperature and reaction time may be adjusted as appropriate depending on the molecular weight or molecular weight distribution of the copolymer obtained. Usually, it is stirred at 0 °C to 150 °C for 1 minute to 100 hours. After completion of the polymerization reaction, the solvent used and the residual vinyl monomer can be removed from the obtained reaction mixture by ordinary separation and purification means, and the target copolymer can be separated.

[0118] The growing end of the copolymer obtained by the polymerization reaction is -TeR derived from the tellurium compound 61 (wherein R 61 is the same as above) and is deactivated by the operation in air after completion of the polymerization reaction, but tellurium atoms may remain. Since the copolymer with tellurium atoms remaining at the end is colored or has poor thermal stability, it is preferable to remove the tellurium atoms. Examples of methods for removing tellurium atoms include radical reduction methods; methods of adsorbing with activated carbon or the like; methods of adsorbing metals with ion exchange resins or the like, and these methods can also be used in combination. The other end (the end opposite to the growing end) of the copolymer obtained by the polymerization reaction is -CR 62 R 63 R 64 (wherein R 62 , R 63 and R 64 are the same as R 62 , R 63 and R 64 in formula (6).).

[0119] (Aqueous dispersion medium) Examples of the aqueous dispersion medium include water or an aqueous solvent (a solvent miscible with water). Specifically, alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, 1-methoxy-2-propanol, 1-butoxy-2-propanol; polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, 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, monoethyl ether; ketones such as acetone, methyl ethyl ketone, isobutyl ketone; amides such as dimethylformaldehyde, dimethylacetamide, etc. Among these, alcohols and glycols are preferred. The aqueous solvent may be used alone or in combination of two or more kinds.

[0120] The content of the aqueous dispersion medium in the coloring composition is not particularly limited and can be adjusted as appropriate. The upper limit value of the content of the aqueous dispersion medium in the coloring composition is usually 99% by mass. Also, considering the viscosity suitable for coating the coloring composition, the lower limit value of the content of the aqueous dispersion medium in the coloring composition is usually 60% by mass, and preferably 80% by mass.

[0121] 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, a fungicide, a viscosity modifier, a pH adjuster, an antifoaming agent, a crosslinking agent, etc.

[0122] (Resin for forming a coating film) The resin for forming the coating film is a component that forms the main body of the film when a coating film is formed using the coloring composition. The resin for forming the coating film is not particularly limited, and those conventionally used in paints can be used. Examples of the coating film-forming resin include thermosetting resins, thermoplastic 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.). The resin for forming the coating film can be used alone or in combination of two or more. When the resin for forming the coating film is blended in the coloring composition, the content of the resin for forming the coating film is preferably 60% by mass to 95% by mass based on the total solid content of the coloring composition.

[0123] (Thermosetting resin, thermoplastic resin) Examples of the thermosetting resin and the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene resin, chlorinated polypropylene resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, urethane resin, phenol resin, polyester resin, acrylic resin, alkyd resin, styrene resin, styrene acrylic resin, polyamide resin, rubber-based resin, cyclized rubber, epoxy resin, celluloses, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin, silicone resin, fluororesin, etc.

[0124] (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 used. Polymers obtained by half-esterifying a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer with a (meth)acrylic compound having a hydroxy group such as hydroxyalkyl (meth)acrylate are also used.

[0125] (Surfactant) Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Examples of nonionic surfactants include fluorosurfactants, silicone surfactants, polyoxyethylene surfactants, and the like. Examples of anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, higher alcohol sulfate esters, aliphatic alcohol sulfate esters, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymer surfactants, and the like. Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, alkylamine salts, and the like. Examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, amino acids, and the like.

[0126] (Leveling agent) Examples of leveling agents include, for example, silicone-based, fluorine-based, etc. Examples of silicone-based 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, fatty acid ester-modified silicone, and the like. Examples of fluorine-based include fluorocarbon-based compounds, fluorosilicone, and the like. These can be used alone or in combination of two or more.

[0127] (Filler) Examples of the filler include silicon dioxide, alumina, zinc white, potassium titanate fiber, aluminum flakes, stainless steel powder, tin powder, gold powder, metal-plated glass powder, titanium mica, calcium carbonate, barium sulfate, barium carbonate, kaolin, barite, clay, and other metal oxides and composite metal oxides. In order to prevent a decrease in viscosity and poor gloss, they can be used alone or in combination of two or more.

[0128] <Method for manufacturing a coloring composition> The coloring composition can be prepared by mixing a coloring agent, a dispersant (block copolymer), an aqueous dispersion medium, and, if necessary, a resin for forming a coating film and other compounding agents. For mixing, for example, a mixing and dispersing machine such as a paint shaker, bead mill, ball mill, dissolver, kneader, etc. can be used. It is preferable to filter the coloring composition after mixing. Examples of the coloring composition include a paint composition for automobiles.

[0129] The coating film can be formed by applying the coloring composition to an untreated body and drying it. The application (coating) of the coloring composition to a body to be treated such as a stainless steel plate or an aluminum plate can be carried out by methods such as roll coating, spin coating, flow coating, slot die coating, spray coating, dip coating, electrodeposition coating, electrostatic coating, brush coating, powder coating, etc. Then, if necessary, heat is applied to evaporate the solvent to form a coating film. At this time, heating or irradiation with ultraviolet rays or the like may be performed. On the coating film obtained by applying the coloring composition, one or more layers of a top clear paint may be further applied to form a top clear coating film. The top clear paint is a liquid paint that forms a colorless or colored transparent coating film mainly composed of a resin component and a solvent, and further containing other paint additives as required.

Examples

[0130] Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples, and can be appropriately modified and implemented without changing the gist thereof. The polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI), amine value, and coating film physical properties of the block copolymer were evaluated according to the following methods.

[0131] The meanings of the abbreviations are as follows. BTEE: Ethyl-2-methyl-2-n-butylteranyl-propionate AIBN: 2,2’-Azobis(isobutyronitrile) ACHN: 1,1’-Azobis(1-cyclohexanecarbonitrile) BA: Butyl acrylate M9EGA: Polyethylene glycol (degree of polymerization = 9) methyl ether acrylate (manufactured by NOF Corporation, Blemmer (registered trademark) AME-400) M11EGA: Polyethylene glycol (degree of polymerization = 11) methyl ether acrylate (manufactured by Green Co., Ltd., KOMERATE-A040TT) St: Styrene BzA: Benzyl acrylate CHA: Cyclohexyl acrylate DMAEMA: Dimethylaminoethyl methacrylate 4VPy: 4-Vinylpyridine PMA: Propylene glycol monomethyl ether acetate MP: 1-Methoxy-2-propanol

[0132] (Polymerization rate) Using a nuclear magnetic resonance (NMR) measuring device (manufactured by Bruker BioSpin, model: AVANCE500 (frequency 500 MHz)), 1 1H-NMR was measured (solvent: CDCl3, internal standard: TMS). For the obtained NMR spectrum, the integration ratio of the peaks derived from the monomer and the peaks derived from the polymer was determined, and the polymerization rate of the monomer was calculated.

[0133] (Weight-average molecular weight (Mw) and molecular weight distribution (PDI)) It was determined by gel permeation chromatography (GPC) using a high-performance liquid chromatograph (manufactured by Tosoh Corporation, model HLC-8320). One SHODEX KF-603 (φ6 mm × 150 mm) (manufactured by SHODEX Corporation) column was used, a lithium bromide (10 mmol / L)-acetic acid (10 mmol / L)-N-methylpyrrolidone solution was used as the mobile phase, and a differential refractometer was used as the detector. The measurement conditions were a column temperature of 40°C, a sample concentration of 20 mg / mL, a sample injection volume of 10 μm, and a flow rate of 0.2 mL / min. A calibration curve was created using polystyrene (molecular weights 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. The molecular weight distribution (PDI = Mw / Mn) was calculated from these measured values.

[0134] (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 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 amine value (B) was calculated by the following formula using the inflection point of the titration pH curve as the titration end point. B = 56.11×Vs×0.1×f / w B: Amine value (mgKOH / g) Vs: Amount of hydrochloric acid (0.1 mol / L)-propanol solution used for titration (mL) f: Normality of hydrochloric acid (0.1 mol / L)-propanol solution w: Mass of measurement sample (g) (in terms of solid content)

[0135] (Blue evaluation) The blue paint (primary color) was applied to a 100-μm transparent film using a 52-μm bar, pre-dried at 60°C, and dried at 140°C for 10 minutes to form a coating film, and a test piece was prepared. The haze of the coating film formation surface of the obtained test piece was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model NDH-5000). Also, a blue paint (aluminum split paint) was applied to a 100-μm transparent film using a 52-μm bar, pre-dried at 60°C, and dried at 140°C for 10 minutes to form a coating film, and a test piece was prepared. Regarding the coating film formation surface of the obtained test piece, measurement was performed using a spectrophotometer (manufactured by Konica Minolta Japan, model CM-2600d), and the chroma was calculated as C = (a 2 + b 2 ) 1 / 2 from the formula.

[0136] (Black evaluation) A black paint was applied to a stainless steel plate using a bar coater (#20), dried at 60°C for 10 minutes to form a coating film, and a test piece was prepared. Regarding the coating film formation surface of the obtained test piece, the L value was measured using an L value measuring instrument (manufactured by Konica Minolta Japan, model CM-2600d) with specular gloss removal. The evaluation was performed on the black paint immediately after preparation and the black paint after being left at 35°C for 3 weeks after adjustment.

[0137] (Synthesis of block copolymer) (Block copolymer No. 1) 9.0 g of BA, 18.0 g of M9EGA, 0.05 g of AIBN, and 6.8 g of PMA were charged into a flask equipped with an argon gas introduction tube and a stirrer. After nitrogen substitution, 0.45 g of BTEE was added, and the mixture was reacted at 60°C for 25 hours to polymerize the A block. The polymerization rate was 95%.

[0138] To the reaction solution, a mixed solution of 5.2 g of BzA, 6.4 g of DMAEMA, 0.05 g of AIBN, and 2.8 g of PMA that had been previously argon-substituted was added, and the mixture was reacted at 60°C for 85 hours to polymerize the B block. The polymerization rate was 88%.

[0139] After completion of the reaction, the reaction solution was poured into stirred n-heptane. The precipitated polymer was suction-filtered and dried to obtain block copolymer No. 1. The obtained block copolymer No. 1 had an Mw of 28,822, a PDI of 1.28, and an amine value of 68 mgKOH / g.

[0140] (Block copolymer Nos. 2 - 6) In the same manner as the production method of block copolymer No. 1, block copolymers Nos. 2 - 6 were prepared. Table 1 shows the monomers, organic tellurium compounds, azo 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 rate of each structural unit in the copolymer was calculated from the charging ratio of the monomers used in the polymerization reaction and the polymerization rate.

[0141] [Table 1]

[0142] [Table 2]

[0143] (Blue paint Nos. 1 - 5) Using the block copolymers Nos. 1, 2, 3, 5, and 6 obtained above as dispersants, blue paints (primary color, aluminum split paint) were prepared. Specifically, each component was put into a 50 mL mayonnaise bottle so as to have the formulation shown in Table 3, and further 66 g of zirconia beads (φ0.3 mm) were added. Using a disperser (manufactured by Ohwell Co., Ltd., SKANDEX DISPERSER BA - S20), stirring was carried out for 5 hours. After the stirring was completed, the beads were filtered off to obtain a pigment dispersion. By mixing the obtained pigment dispersion with a clear paint or the pigment dispersion with aluminum primary color, blue paints Nos. 1 - 5 (primary color, aluminum split paint) were prepared. Regarding the obtained blue paints Nos. 1 - 5, it was visually confirmed that the dispersibility of the blue pigment was good.

[0144] [Table 3] Blue pigment: Trade name "CYANINE Blue G - 314R", manufactured by Sanyo Shikiso Co., Ltd., chlorinated copper phthalocyanine pigment (C.I.Pigment Blue15:1) Defoaming agent: silicone - based surfactant, trade name "BYK - 024", manufactured by BYK Chemie Acrylic resin: Manufactured by DIC Corporation, Waterzole (registered trademark) ACD-2001, non-volatile content: 40% by mass, solvent: water, propylene glycol-n-butyl ether Melamine resin: Methylated melamine resin, manufactured by allnex, product name "Cymel (registered trademark) 303LF", non-volatile content: 100% by mass Water-based aluminum: Product name "STAPA IL HYDROLAN S 412", manufactured by ECKART, aluminum paste

[0145] (Blue paint Nos. 6-8) As a dispersant, block copolymers No. 1, 4, and 5 obtained above were used to prepare blue paints (primary colors, aluminum split paints). Specifically, each component was put into a 50 mL mayonnaise bottle so as to have the formulation shown in Table 4, and further 66 g of zirconia beads (φ0.3 mm) were added. Using a disperser (manufactured by Aurwell, SKANDEX DISPERSER BA-S20), stirring was carried out for 5 hours. After completion of stirring, the beads were filtered off to obtain a pigment dispersion. By mixing the obtained pigment dispersion with a clear paint or the pigment dispersion with aluminum primary color, blue paints No. 6-8 (primary colors, aluminum split paints) were prepared. Regarding the obtained blue paints No. 6-8 (primary colors, aluminum split paints), it was visually confirmed that the dispersibility of the blue pigment was good.

[0146]

Table 4

[0147] (Black paints No. 1 to 5) Using the block copolymers No. 1, 2, 3, 5, and 6 obtained above as dispersants, black paints were prepared. Specifically, each component was put into a 50 mL mayonnaise bottle so as to have the formulation shown in Table 5, and further 66 g of zirconia beads (φ0.3 mm) were added. Using a disperser (manufactured by Owel, SKANDEX DISPERSER BA-S20), stirring was carried out for 5 hours. After the stirring was completed, the beads were filtered off to obtain a pigment dispersion. By mixing the obtained pigment dispersion and a clear paint, black paints No. 1 to 5 were prepared. For the obtained black paints No. 1 to 5, it was visually confirmed that the dispersibility of carbon black was good.

[0148]

Table 5

[0149] Block copolymers No. 1 to 3 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. The haze values of the coating films formed from blue paints No. 1 to 3, 6 (primary colors) containing these block copolymers No. 1 to 3 were low. Also, the chroma of the coating films formed from blue paints No. 1 to 3, 6 (aluminum split paints) was high.

[0150] Furthermore, for the black paints No. 1 to 3 using these block copolymers No. 1 to 3, the L values of the prepared paint films were low both immediately after preparation and after 3 weeks of storage. Therefore, these block copolymers No. 1 to 3 have high dispersion performance for both blue colorants and black colorants.

[0151] Block copolymers No. 4 to 6 are the cases where they do not have a B block containing a structural unit represented by the formula (3). The chroma of the paint films formed from the blue paints No. 4, 5, 7, 8 (aluminum split paints) using these block copolymers No. 4 to 6 was low.

Industrial Applicability

[0152] The coloring composition of the present invention is useful for automotive paints and the like because the transparency and chroma of the formed paint film are high.

Claims

1. A coloring composition containing a blue coloring material, a dispersant, an aqueous dispersion medium, and a resin for forming a coating film, wherein the dispersant contains 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, and has a weight average molecular weight (Mw) of 3,000 to 40,000. 【Chemical Formula 1】 [In formula (1), n1 represents an integer of 2 to 30. R 11 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 12 represents an alkylene group having 1 to 3 carbon atoms. R 13 represents a hydrogen atom or a methyl group. In addition, a plurality of R 12 may be the same or different from each other. ] 【Chemical Formula 2】 [In formula (3), R 31 represents an aromatic group which may have a substituent. n3 represents 0 or 1. Z 3 represents O or NH. R 32 represents a hydrogen atom or a methyl group. ]

2. The coloring 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. The coloring composition according to claim 1 or 2, 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, 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 0.15 to 4.

0.

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

6. The coloring composition according to any one of claims 1 to 5, wherein the amine value of the block copolymer is 10 mgKOH / g to 200 mgKOH / g.

7. The coloring 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). 【Chemical Formula 4】 [In formula (4), R 41 and R 42 each independently represent a linear or cyclic hydrocarbon group which may have a substituent. R 41 and R 42 may be bonded to each other to form a cyclic structure. R 43 represents a divalent hydrocarbon group. Z 4 represents O or NH. R 44 represents a hydrogen atom or a methyl group.]

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

9. The coloring 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 coloring composition according to any one of claims 1 to 9, wherein the block copolymer is polymerized by living radical polymerization.

11. The coloring composition according to any one of claims 1 to 10, wherein the blue coloring material is a phthalocyanine-based pigment.

12. The coloring composition according to any one of claims 1 to 11, which is an automotive paint composition.

13. A coating film formed from the coloring composition according to any one of claims 1 to 12.

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