TW201945506A - Dispersant composition, coloring composition and color filter - Google Patents

Abstract

The purpose of the present invention is to provide a dispersant composition which exhibits excellent pigment dispersibility. A dispersant composition according to the present invention is characterized by being obtained by mixing: (a) a block copolymer which has a block A having an acidic group and a block B containing structural units represented by general formulae (1) and (2); (b) an aromatic compound; and (c) a tertiary amine compound. (In formulae (1) and (2), each of R11, R12, R13, R21 and R22 independently represents an optionally substituted chain or cyclic hydrocarbon group; two or more of the R11, R12 and R13 moieties may combine with each other to form a cyclic structure; the R21 and R22 moieties may combine with each other to form a cyclic structure; each of R14 and R23 represents a hydrogen atom or a methyl group; each of X1 and X2 represents a divalent linking group; and Y- represents a counter ion.).

Description

Dispersant composition, coloring composition, and color filter

The present invention relates to a dispersant composition, a coloring composition containing the dispersant composition, and a color filter including a coloring layer formed using the coloring composition.

Conventionally, when manufacturing a color filter used for a liquid crystal display or the like, a method for imparting a coloring material to a substrate is known as a pigment dispersion method, a dyeing method, an electrophotographic method, and a printing method. Among these, the pigment dispersion method is widely used from the viewpoints of spectral characteristics, durability, pattern shape, and accuracy. In the pigment dispersion method, for example, a coating film composed of a coloring composition such as a mixed pigment, a dispersant, and a dispersant (solvent) is formed on a substrate, exposed through a photomask having a desired pattern shape, and subjected to alkaline development.

In recent years, color filters have been required to have higher transmission, high brightness, high contrast, and high color gamut. Therefore, various reviews have been conducted, such as increasing the concentration of pigments in coloring compositions, or developing pigments with inherent transmission absorption spectra that are consistent with the fluorescent spectrum of backlights.

In particular, regarding the enhancement of the brightness of green pixels, for example, as described in Patent Documents 1 and 2, a novel zinc halide phthalocyanine green pigment having a specific hue has been proposed. This makes it possible to achieve higher brightness than conventional copper halide phthalocyanin green pigments. Further, Patent Document 3 discloses the use of a dispersant having a structure unit derived from a vinyl monomer having a tertiary amine group and a structure derived from a vinyl monomer having a quaternary ammonium salt group. Unit, the quaternary ammonium salt group contains less than 60 mole% of the total content of the tertiary amine group and the quaternary ammonium salt group.
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-70342.
[Patent Document 2] Japanese Patent Laid-Open No. 2004-70343.
[Patent Document 3] Japanese Patent Application Publication No. 2016-38584.

[Problems to be solved by the invention]
However, if the pigments described in Patent Documents 1 and 2 are used, the viscosity of the pigment dispersion liquid is increased, and it is difficult to industrially use the pigment dispersion liquid to produce a colored resin composition. Further, in the dispersant used in the method of Patent Document 3, the pigment dispersibility is insufficient. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a dispersant composition having excellent pigment dispersibility.
[Technical means to solve problems]

The dispersant composition of the present invention which can solve the above-mentioned problems is a mixture of (a), (b), and (c), (a) a block copolymer having an A block and a B block, and the A block A structural unit derived from a vinyl monomer having an acidic group, and the B block contains a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); At least one type of aromatic compound selected from the group consisting of a group of diamine carboxylic acid imine, an aromatic compound containing an acidic group, and an aromatic compound containing a phenolic hydroxyl group; (c) a tertiary amine compound.

[Chemical Formula 1]
[In formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion. A

[Chemical Formula 2]
[In formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a ring structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. A
[Contrast with the effect of the prior art]

By using the dispersant composition of the present invention, a colored composition having a high dispersibility of a coloring material and a low viscosity can be obtained. In particular, when a cyclic fluorene compound is used as the (c) tertiary amine compound, the brightness of the coating film formed by the coloring composition can also be increased.

The dispersant composition of the present invention is a mixture of (a), (b), and (c). (A) a block copolymer having an A block and a B block. A structural unit of an acidic vinyl monomer, the B block contains a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); (b) an aromatic dicarboxylic acid sulfonium imine At least one aromatic compound selected from the group consisting of an acidic group-containing aromatic compound and a phenolic hydroxyl group-containing aromatic compound; (c) a tertiary amine compound.

(a) Block copolymer The dispersant composition contains (a) a block copolymer. The aforementioned (a) block copolymer may be blended with only one kind or in combination with two or more kinds. The (a) block copolymer has an A block and a B block, the A block contains a structural unit derived from a vinyl monomer having an acidic group, and the B block contains the formula (1) described later A structural unit and a structural unit represented by the following general formula (2).

In the present invention, the "A block" may also be referred to as "A section", and the "B block" may also be referred to as "B section". In the present invention, "vinyl monomer" means a monomer having a free-radically polymerizable carbon-carbon double bond in the molecule. The "structural unit derived from a vinyl monomer" refers to a radical-polymerizable carbon-carbon double bond polymerization of a vinyl monomer to become a carbon-carbon single bond. "(Meth) acrylic acid" is "at least one of acrylic acid and methacrylic acid". "(Meth) acrylate" is "at least one of acrylate and methacrylate". "(Meth) acrylfluorenyl" is "at least one of acrylmethyl and methacrylmethyl".

(A block)
The A block is a polymer block and has a structural unit derived from an acidic vinyl monomer. The A block has an acidic group, whereby alkaline development is easy. Therefore, the aforementioned block copolymer is suitable for use in a coloring composition for color filters used in the production of color filters by alkaline development.

Examples of the acidic group include a carboxyl group (-COOH), a sulfonic acid group (-SO ₃ H), a phosphate group (-OPO ₃ H ₂ ), a phosphonic acid group (-PO ₃ H ₂ ), and a phosphonic acid group (-PO ₂ H ₂ ). The A block may have only one structural unit derived from a vinyl monomer having an acidic group, or may have two or more structural units derived from a vinyl monomer having an acidic group.

The vinyl monomer having an acidic group is preferably at least one selected from a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, or a vinyl monomer having a phosphate group. Among these, at least one selected from (meth) acrylic monomers having a carboxyl group, (meth) acrylic monomers having a sulfonic group, or (meth) acrylic monomers having a phosphate group is preferred.

Examples of vinyl monomers having a carboxyl group include (meth) acrylic acid; 2- (meth) acryloxyethyl succinate, 2- (meth) acryloxyethyl maleate, and o-benzene Vinyl monomers having a hydroxyl group such as 2- (meth) acryloxyethyl diformate (preferably hydroxyalkyl (meth) acrylate) make anhydrides such as maleic anhydride, succinic anhydride, and phthalic anhydride Reacting monomers; crotonic acid; maleic acid;

Examples of the vinyl monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, ethyl (meth) acrylate disulfonate, (meth) acrylamide, methyl sulfonic acid, and ethyl sulfonic acid. Ester (meth) acrylamide and the like.

Examples of the vinyl monomer having a phosphate group include 2- (phosphinofluorenyloxy) ethyl (meth) acrylate and the like.

The content of the structural unit derived from the vinyl monomer having an acidic group is preferably 2 mass% or more, more preferably 5 mass% or more, and still more preferably 7 mass% or more, out of 100 mass% of the A block. It is preferably 20% by mass or less, more preferably 18% by mass or less, and still more preferably 16% by mass or less. If the content rate of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate when the alkali is neutralized during alkali development is fast, and if it is 20% by mass or less, the hydrophilicity will not be changed. If it is too high, the formed pixels can be suppressed from being cluttered.

The A block may have a structural unit other than a structural unit derived from an acidic vinyl monomer. The other structural units that may be contained in the A block are not particularly limited as long as they are formed by a vinyl monomer copolymerizable with both a vinyl monomer having an acidic group and a vinyl monomer forming a B block described later. . The vinyl monomers of the A block that can form other structural units can be used alone or in combination of two or more.

Specific examples of the vinyl monomer that can form other structural units in the A block include α-olefins, aromatic vinyl monomers, heterocyclic vinyl monomers, vinylamines, vinyl carboxylates, Olefins, (meth) acrylic monomers, etc. These vinyl monomers may have a hydroxyl group or an epoxy group.

Examples of the α-olefin include 1-hexene, 1-octene, and 1-decene.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, and 2-hydroxyl. Methylstyrene, 1-vinylnaphthalene and the like.
Examples of the heterocyclic-containing vinyl monomer include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 2-vinylpyridine, and 4-vinylpyridine.
Examples of the vinylfluorenamine include N-vinylformamide, N-vinylacetamide, 1-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, and the like.
Examples of vinyl carboxylate include vinyl acetate, trimethyl vinyl acetate, and vinyl benzoate.
Examples of the diene include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, and the like.

Examples of the (meth) acrylic monomer include (meth) acrylic acid esters having a linear alkyl group (straight chain or branched alkyl group); and (meth) acrylic acid having a cyclic alkyl group (monocyclic structure). Esters; (meth) acrylates with aromatic ring groups; (meth) acrylamide; (meth) acrylates with polyalkylene glycol building blocks; (meth) acrylates with hydroxyl groups; lactone modification (Meth) acrylates with hydroxyl groups; (meth) acrylates with alkoxy groups; (meth) acrylates with cyclic ether groups, etc.

Examples of the (meth) acrylate having a chain alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl methacrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Examples of the (meth) acrylate having a cyclic alkyl group include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and cyclododecyl (meth) acrylate. Examples of the (meth) acrylate having an aromatic ring group include benzyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate.

Examples of (meth) acrylamide are (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (Meth) acrylamide and the like.
Examples of the (meth) acrylate having a polyalkylene glycol structural unit include polyethylene glycol (degree of polymerization = 2 to 10), methyl ether (meth) acrylate, and polyethylene glycol (degree of polymerization = 2 to 10) ) Ethyl ether (meth) acrylate, polyethylene glycol (degree of polymerization = 2 to 10), propyl ether (meth) acrylate, polyethylene glycol (degree of polymerization = 2 to 10), phenyl ether (methyl ether) (Meth) acrylate and other (meth) acrylates with polyethylene glycol structural units; polypropylene glycol (polymerization degree = 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree = 2 to 10) Ethyl ether (meth) acrylate, polypropylene glycol (polymerization degree = 2 to 10), propyl ether (meth) acrylate, polypropylene glycol (polymerization degree = 2 to 10), phenyl ether (meth) acrylate, etc. (Meth) acrylic acid esters having polypropylene glycol structural units.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic acid Hydroxyalkyl (meth) acrylate and the like such as 4-hydroxybutyl.

The lactone-modified (meth) acrylic acid ester having a hydroxyl group includes a case where the (meth) acrylic acid ester having a hydroxyl group is added to a lactone, and a caprolactone is preferably added. The lactone addition amount is preferably 1 mol to 10 mol, and more preferably 1 mol to 5 mol. Examples of the lactone-modified (meth) acrylate having a hydroxyl group include 1 mol adduct of 2-hydroxyethyl (meth) acrylate, and caprolactone 2-hydroxyethyl (meth) acrylate. 2 mol adduct, 2-mole caprolactone (meth) acrylate 3 mol adduct, 2-mole caprolactone (meth) acrylate 4 mol adduct, 2- (meth) acrylic acid 2- 5 mol adduct of caprolactone of hydroxyethyl ester, 10 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, and the like.

Examples of the (meth) acrylate having an alkoxy group include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and phenoxyethyl (meth) acrylate.

Examples of the (meth) acrylate having a cyclic ether group include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acryloylmorpholine, and (meth) acrylic acid. 2- (4-morpholinyl) ethyl ester, (3-ethyloxetan-3-yl) methyl (meth) acrylate, (2-methyl-2-ethyl) (meth) acrylate -1,3-dioxocyclopentane-4-yl) methyl ester, cyclic trimethylolpropane formal (meth) acrylate, 2-[(2-tetrahydropyranyl) ) Oxy] ethyl, 1,3-dioxane- (meth) acrylate, and the like.

The vinyl monomer that can form other structural units that the A block can contain is preferably a (meth) acrylic monomer, more preferably a (meth) acrylate having a chain alkyl group, and ( (Meth) acrylates, (meth) acrylates with polyalkylene glycol structural units, (meth) acrylates with hydroxyl groups, lactones modified (meth) acrylates with hydroxyl groups, cyclic ether groups At least one selected from the group consisting of (meth) acrylates. The vinyl monomers usable in the A block may be used alone or in combination of two or more.

The A block is derived from the group consisting of a (meth) acrylate having a chain alkyl group, a (meth) acrylate having a cyclic alkyl group, and a (meth) acrylate having an aromatic ring group. When selecting at least one vinyl monomer structural unit, the total content of these structural units is preferably 30% by mass or more, more preferably 35% by mass or more, and more preferably 40% by mass of the A block 100% by mass. Above mass%, more preferably above 50% by mass, even more preferably above 60% by mass, particularly preferably above 70% by mass, more preferably below 98% by mass, even more preferably below 95% by mass, and more It is preferably 90% by mass or less.

The A block is derived from (meth) acrylamide, (meth) acrylate with a polyalkylene glycol structural unit, (meth) acrylate with a hydroxyl group, and (methyl) modified with a lactone. (Meth) acrylates, (meth) acrylates with alkoxy groups, and (meth) acrylates with cyclic ether groups when the structural units of at least one vinyl monomer are selected, such structures The total content of the units is preferably 2% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 70% by mass or less, and more preferably 65% by mass of the A block 100% by mass. Mass% or less, more preferably 60 mass% or less, still more preferably 50 mass% or less, still more preferably 30 mass% or less, and particularly preferably 20 mass% or less.

The A block preferably does not have an amine group. That is, it is preferable that the vinyl monomer which comprises A block does not contain the vinyl monomer which has an amine group. When a large number of amine groups are present in the A block, when a dispersant is used as the coloring material, the coloring material is adsorbed on both the A block and the B block, and the dispersing performance of the coloring material is reduced. In the A block, the content rate of the structural unit derived from the vinyl monomer having an amine group is preferably 2% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, and most preferably 0% by mass.

When the A block contains two or more kinds of structural units, various structural units contained in the A block may be contained in the A block in any form such as random copolymerization and block copolymerization. From the viewpoint of uniformity, it is preferable Contained in a random copolymer state. For example, the A block can be formed by a copolymer of a structural unit composed of an a1 block and a structural unit composed of an a2 block.

(B block)
The B block is a polymer block and has a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2). The B block has a quaternary ammonium salt group in addition to the tertiary amine group, so it has high affinity with the coloring material.

(Construction unit represented by general formula (1))
The structural unit represented by the general formula (1) has a quaternary ammonium salt in the structure. The structural unit represented by the general formula (1) in the B block may have only one kind or two or more kinds.

[Chemical Formula 3]
[In formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion. A

The chain hydrocarbon group represented by R ¹¹ to R ¹³ includes a linear chain and a branched chain. Examples of the substituent possessed by the chain hydrocarbon group represented by R ¹¹ to R ¹³ include a halogen group, an alkoxy group, a benzamidine group (-COC ₆ H ₅ ), a hydroxyl group, and the like. Examples of the substituent possessed by the cyclic hydrocarbon group represented by R ¹¹ to R ¹³ include a chain alkyl group, a halogen atom, an alkoxy group, and a hydroxyl group.

The aforementioned groups represented by R ¹¹ to R ^{13 are} preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, and an aralkyl group having 7 to 16 carbon atoms which may have a substituent, and more preferably a methyl group, an ethyl group, Propyl, benzyl (-CH ₂ C ₆ H ₅ ).

The cyclic structure formed by two or more of R ¹¹ to R ¹³ bonded to each other may be, for example, a nitrogen-containing monocyclic heterocyclic ring of 5 to 7 member rings or a condensed ring formed by condensation of two of these. The nitrogen-containing heterocyclic ring preferably has no aromaticity, and is more preferably a saturated ring. Specific examples include structures represented by the following formulae (1-1), (1-2), and (1-3).

[Chemical Formula 4]
[In the general formulae (1-1), (1-2), and (1-3), R ¹⁵ is any one of R ¹¹ to R ¹³ . R ¹⁶ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer from 0 to 5. m represents an integer from 0 to 4. n represents an integer from 0 to 4. * Indicates bonding. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, R ^{16 in the} plural may be the same or different. A

Examples of the divalent linking group X ¹ in the general formula (1) include an alkylene group, an arylene group, a -CONH-R ¹⁷ -yl group (fluorenylamino), and a -COO-R ¹⁸ -yl group having 1 to 10 carbon atoms. (Ester group) and the like are preferably a -CONH-R ¹⁷ -group and / or a -COO-R ¹⁸ -group, and more preferably a -COO-R ¹⁸ -group. The bonding direction of the fluorenylamino group and the ester group is not particularly limited, but the fluorenylamino group is preferably C-CO-NH-R ¹⁷ -N ⁺ R ¹¹ R ¹² R ¹³ and the ester group is bonded. The aspect is preferably C-CO-OR ¹⁸ -N ⁺ R ¹¹ R ¹² R ¹³ .

The aforementioned R ¹⁷ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably Alkyl group having 1 to 4 carbon atoms. Specific examples include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and heptamethylene.

The aforementioned R ¹⁸ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably Alkyl group having 1 to 4 carbon atoms. Specific examples include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and heptamethylene.

Y ^- include a halogen anion, carboxylate anion, nitroxide radical anion, sulfate anion, a sulfonate anion, phosphate anion and the like.

Examples of the halogen anion include a fluorine anion, a chloride anion, a bromine anion, and an iodine anion.
Examples of the carboxylate anion include alkyl carboxylate anions such as acetic acid anion and propionate anion; and aromatic carboxylate anions such as benzoic acid anion.
Examples of the sulfate anion include alkyl sulfate anions such as methyl sulfate anion and ethyl sulfate anion; and aromatic sulfate anions such as phenyl sulfate anion and benzyl sulfate anion.
Examples of the sulfonate anion include alkylsulfonate anions such as methanesulfonic acid anion and ethanesulfonic acid anion; and aromatic sulfonate anions such as benzenesulfonic acid anion and toluenesulfonic acid anion.
Examples of the phosphate anion include an alkyl phosphate anion such as a methyl phosphate anion; and an aromatic phosphate anion such as a phenyl phosphate anion.

Specific examples of the vinyl monomer that forms the structural unit represented by the formula (1) include (meth) acrylic acid ethoxyethyltrimethylammonium chloride and (meth) acrylic acid oxypropyltrimethyl Ammonium chloride, (meth) acryloxybutyltrimethylammonium chloride, (meth) acryloxyethylbenzyldimethylammonium chloride, (meth) acryloxypropyl Benzyldimethylammonium chloride, (meth) acryloxybutylbenzyldimethylammonium chloride, (meth) acryloxyethylbenzyldiethylammonium chloride, (formaldehyde) (Propyl) propenyloxypropylbenzyldiethylammonium chloride, (meth) propenyloxybutylbenzyldiethylammonium chloride, (meth) propenylmethylaminopropylpropylbenzyldichloride Methyl ammonium chloride, (meth) acryloxyethyltrimethylammonium bromide, (meth) acryloxypropyltrimethylammonium bromide, (meth) acryloxybutyloxybutyl Trimethylammonium bromide, (meth) acryloxyethylbenzyldimethylammonium bromide, (meth) acryloxypropylbenzyldimethylammonium bromide, (meth) propylene Ethoxybutylbenzyldimethylammonium bromide, (meth) acryloxyethylbenzyldiethylammonium bromide, (formyl ) Acrylic acid oxypropyl benzyl diethylammonium bromide, (meth) acrylic acid oxybenzyl diethyl ammonium bromide, (meth) acrylic acid fluorenyl amine aminopropyl benzyl dimethyl Ammonium bromide, (meth) acryloxyethyltrimethylammonium iodide, (meth) acryloxypropyltrimethylammonium iodide, (meth) acryloxybutyltrimethylammonium iodide Methyl ammonium iodide, (meth) acryloxyethylbenzyldimethylammonium iodide, (meth) acryloxypropylbenzyldimethylammonium iodide, (meth) acrylic acid Oxybutyl benzyl dimethyl ammonium iodide, (meth) acryl ethoxy benzyl diethyl ammonium iodide, (meth) acryl ethoxy propyl benzyl diethyl ammonium iodide (Meth) acryloxybutylbenzyldiethylammonium iodide, (meth) acryloxyethyltrimethylammonium fluoride, (meth) acryloxypropyltrimethylammonium fluoride Ammonium fluoride, (meth) acryloxybutyl trimethylammonium fluoride, (meth) acryloxyethyl benzyldimethylammonium fluoride, (meth) acryloxypropyl Benzyldimethylammonium fluoride, (meth) acryloxybutylbenzyldimethylammonium fluoride, (meth) acryloxyethyl Diethylammonium fluoride, (meth) acryloxypropylbenzyldiethylammonium fluoride, (meth) acryloxybutylbenzyldiethylammonium fluoride, (methyl) Propylene ethoxyethyltrimethylammonium = methyl sulfate, (meth) propylene ethoxypropyltrimethylammonium = methylsulfate, (meth) propylene ethoxybutyltrimethylammonium = Methyl sulfate, (meth) acryloxyethyl dimethylethylammonium = ethyl sulfate, (meth) acryloxypropyl dimethylethylammonium = ethyl sulfate, (Meth) acryloxybutyldimethylethylammonium = ethyl sulfate, (meth) acryloxyethyltrimethylammonium = toluene-4-sulfonate, (meth) propylene Ethoxypropyltrimethylammonium = toluene-4-sulfonate, (meth) acrylic acid oxybutyltrimethylammonium = toluene-4-sulfonate, (meth) acrylfluorenylamine Propyltrimethylammonium = methylsulfate, (meth) acrylfluorenylamidopropylethyldimethylammonium = ethylsulfate, and the like.

The content of the structural unit represented by the general formula (1) is preferably 30% by mass or more, more preferably 35% by mass or more, more preferably 40% by mass or more, and more preferably 85% by mass of the B block 100% by mass. % Or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, still more preferably 60% by mass or less, and still more preferably 50% by mass or less. By making the content rate of the structural unit represented by General formula (1) into this range, it has high affinity with a coloring material.

(Construction unit represented by general formula (2))
The structural unit represented by the general formula (2) has a tertiary amine structure. In the B block, the structural unit represented by the general formula (2) may have only one kind or two or more kinds.

[Chemical Formula 5]
[In formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a ring structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. A

The chain hydrocarbon group represented by R ²¹ or R ²² includes a linear chain and a branched chain. Examples of the substituent possessed by the chain hydrocarbon group represented by R ²¹ or R ²² include a halogen group, an alkoxy group, a benzamidine group, and a hydroxyl group. Examples of the substituent possessed by the cyclic hydrocarbon group represented by R ²¹ or R ²² include a chain alkyl group, a halo group, an alkoxy group, and a hydroxyl group.

The aforementioned group represented by R ²¹ or R ²² is preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, and an aralkyl group having 7 to 16 carbon atoms which may have a substituent, and more preferably methyl, ethyl, Propyl, benzyl.

The aforementioned cyclic structure formed by bonding R ²¹ or R ^{22 to} each other may be, for example, a nitrogen-containing single heterocyclic ring having 5 to 7 member rings or a condensed ring formed by condensation of two of these. The nitrogen-containing heterocyclic ring preferably has no aromaticity, and is more preferably a saturated ring. Specific examples include structures represented by the following formulae (2-1), (2-2), and (2-3).

[Chemical Formula 6]
[In the general formulae (2-1), (2-2), and (2-3), R ²⁴ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer from 0 to 5. m represents an integer from 0 to 4. n represents an integer from 0 to 4. * Indicates bonding. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, the R ^{24s in the} plural may be the same or different, respectively. A

Examples of the divalent linking group X ² in the general formula (2) include an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH-R ²⁵ -group (fluorenylamino group), and -COO-R ^26- Group (ester group) and the like, preferably -COO-R ²⁶ -group and / or -CONH-R ²⁵ -group, more preferably -CONH-R ²⁵ -group and / or -COO-R ²⁶ -group, and More preferably, it is -COO-R ²⁶ -based. The bonding direction of the fluorenylamino group and the ester group is not particularly limited. The fluorenylamino group is preferably C-CO-NH-R ²⁵ -NR ²¹ R ²² , and the ester group is more preferably C-CO-OR ²⁶ -NR ²¹ R ²² .

The aforementioned R ²⁵ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably Alkyl group having 1 to 4 carbon atoms. Specific examples include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and heptamethylene.

The aforementioned R ²⁶ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably Alkyl group having 1 to 4 carbon atoms. Specific examples include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and heptamethylene.

The content of the structural unit represented by the general formula (2) is preferably 15% by mass or more, more preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 100% by mass of the B block. 30 mass% or more, particularly preferably 40 mass% or more, preferably 70 mass% or less, more preferably 65 mass% or less, and still more preferably 60 mass% or less. When the content rate of the structural unit represented by General formula (2) exists in this range, it has high affinity with a coloring material by this.

The B block may contain only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may contain other structural units. From the viewpoint of maintaining affinity with the coloring material, the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the B block is preferably 80% by mass or more, more It is preferably 90% by mass or more, and more preferably 95% by mass or more. The B block preferably does not substantially contain a structural unit derived from a vinyl monomer having an acidic group. That is, the content of the structural unit derived from the vinyl monomer having an acidic group is preferably 5 mass% or less, more preferably 3 mass% or less, out of 100 mass% of the B block.

Specific examples of the vinyl monomer that can form the other structural unit of the B block include the same examples as those of the vinyl monomer that can form the other structural unit of the A block.

When the B block contains two or more structural units, various structural units contained in the B block can be contained in the B block in any form such as random copolymerization and block copolymerization. From the viewpoint of uniformity, it is preferable Contained in a random copolymer state. For example, the B block can be formed by a copolymer of a structural unit composed of a b1 block and a structural unit composed of a b2 block.

(Block copolymer)
The structure of the block copolymer is preferably a linear block copolymer. The linear block copolymer may have any structure (collocation), but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the A block is represented by A and the B block is represented by B. , It is preferable to have at least a group selected from the group consisting of (AB) _m -type, (AB) _m- A-type, and (BA) _m- B-type (m is an integer of 1 or more, for example, an integer of 1 to 3). A structured copolymer. Among these, from the viewpoints of handleability during processing and physical properties of the composition, a diblock copolymer represented by AB is preferable among these. By constituting the diblock copolymer shown in AB, it is possible to have the structural unit derived from the vinyl monomer having an acidic group in the A block and the ethylene derived from the tertiary amine group in the B block. The structural unit of the base monomer and the structural unit derived from the vinyl monomer having a quaternary ammonium salt group are localized, and can effectively act on the coloring material, the solvent, and the binder resin (alkali soluble resin).

The content of the A block is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass, and still more preferably 50% by mass or more in the entire 100% by mass of the block copolymer. It is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and still more preferably 65% by mass or less. The content of the B block is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and still more preferably 30% by mass or more in the entire 100% by mass of the block copolymer. It is preferably 65% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, still more preferably 50% by mass or less, and particularly 45% by mass or less. By adjusting the content ratio of the A block and the B block to be within the above range, it is possible to balance both heat resistance and dispersibility when used as a dispersant.

In the block copolymer, the mass ratio of A block to B block (A block / B block) is preferably 50/50 or more, more preferably 55/45 or more, and still more preferably 60/40 or more. It is preferably 95/5 or less, more preferably 90/10 or less, still more preferably 80/20 or less, and still more preferably 70/30 or less. When the mass ratio of the A block and the B block is within the aforementioned range, the dispersing performance and the alkali developability when used as a dispersant can be balanced.

In the aforementioned (a) block copolymer, the content rate of the structural unit derived from the vinyl monomer having an acidic group is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 4% by mass. The above is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

In the (a) block copolymer, the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) is preferably 5% by mass or more, and more preferably 10% by mass or more. It is more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less.

The molecular weight of the (a) block copolymer was measured by a gel permeation chromatography (hereinafter referred to as "GPC") method. The weight average molecular weight (Mw) of the aforementioned (a) block copolymer is preferably 5,000 or more, more preferably 6000 or more, still more preferably 7,000 or more, preferably 15,000 or less, more preferably 12,000 or less, and even more preferably Below 10000. When the weight average molecular weight is within the above range, the dispersibility when used as a dispersant is better.

The molecular weight distribution (PDI) of the (a) block copolymer is preferably 2.0 or less, more preferably 1.6 or less, and still more preferably 1.4 or less. In the present invention, the molecular weight distribution (PDI) is a value obtained by (weight average molecular weight (Mw) of block copolymer) / (number average molecular weight (Mn) of block copolymer). The smaller the PDI, the narrower the molecular weight distribution width. It is a copolymer with concentrated molecular weight. When the value is 1.0, the molecular weight distribution width is the narrowest. That is, the lower limit of PDI is 1.0. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.0, the molecular weight distribution (PDI) of the block copolymer includes those having a small molecular weight and those having a large molecular weight.

(Manufacturing method of block copolymer)
Examples of the method for producing the aforementioned block copolymer include: a method of producing A block first by polymerizing a vinyl monomer, and then polymerizing a block of B block in A block; A method for polymerizing the A block monomers in the B block; a method for coupling the A block and the B block after separately producing the A block and the B block; firstly manufacturing the A block, and then polymerizing the A method of forming a monomer composition of a vinyl monomer of a structural unit represented by the formula (2), and then quaternizing the tertiary amine structure of a part of the structural unit represented by the formula (2) in the obtained polymer; polymerization may form The monomer composition of the vinyl monomer of the structural unit represented by the formula (2), the monomer of the A block is polymerized in the polymer, and the tertiary amine structure of a part of the structural unit represented by the formula (2) in the obtained polymer is carried out A method of quaternization; separately producing A blocks and blocks having a structural unit represented by formula (2), and coupling these blocks to obtain a tertiary amine part of the structural unit represented by formula (2) in the obtained polymer Construct a method of quaternization, etc.

The polymerization method is not particularly limited, and living radical polymerization is preferred. That is, the block copolymer is preferably one polymerized by living radical polymerization. In the conventional radical polymerization method, not only the start of the reaction and the growth reaction will cause the inactivation of the growth terminal, but also the stop of the reaction and the chain transfer reaction will also cause the inactivation of the growth terminal. It is likely to be a mixture of polymers with various molecular weights and uneven compositions. The tendency. In this regard, in addition to maintaining the simplicity and versatility of conventional radical polymerization methods, it is not easy to cause stop reactions or chain transfers, and it can grow without inactivation at the growth end, so it is easy to produce a molecular weight distribution with precise control and composition A homogeneous polymer is preferred in this regard.

Among the living radical polymerization methods, a method using a transition metal catalyst (ATRP method), a method using a sulfur-based reversible chain transfer agent (RAFT method), and an organic tellurium compound are used in order to stabilize the polymerization growth end by different methods. Method (TERP method) and other methods. The ATRP method uses an amine complex, so it may not be possible to use an acidic group that does not protect an acidic vinyl monomer. The RAFT method is difficult to form a low molecular weight distribution when using a plurality of monomers, and has defects such as sulfur odor and coloring. Among these methods, the TERP method is preferably used from the viewpoint that monomer diversity, molecular weight control in the polymer field, uniform composition, or coloring can be used.

The TERP method refers to a method of polymerizing a radical polymerizable compound (vinyl monomer) using an organic tellurium compound as a polymerization initiator, for example, 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 TERP polymerization method include the following (a) to (d).
(a) A vinyl monomer is polymerized using an organic tellurium compound represented by the general formula (11).
(b) Polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (11) and an azo-based polymerization initiator.
(c) Polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (11) and an organic ditelluride compound represented by the general formula (12).
(d) Polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (11) and an azo-based polymerization initiator and an organic ditelluride compound represented by the general formula (12).

[Chemical Formula 7]
[In the general formula (11), R ¹ represents an alkyl group, an aryl group, or an aromatic heterocyclic group having 1 to 8 carbon atoms. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, fluorenyl group, fluorenylamino group, oxycarbonyl group, cyano group, allyl group, or propargyl group having 1 to 8 carbon atoms.
In the general formula (12), R ¹ represents an alkyl group, an aryl group, or an aromatic heterocyclic group having 1 to 8 carbon atoms. ]

The group represented by R ¹ is an alkyl group, an aryl group, or an aromatic heterocyclic group having 1 to 8 carbon atoms, and is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, pentyl, hexyl, and heptyl. Linear or branched alkyl such as octyl, or cyclic alkyl such as cyclohexyl. A linear or branched alkyl group having 1 to 4 carbon atoms is preferred, and a methyl or ethyl group is more preferred.
Examples of the aryl group include a phenyl group and a naphthyl group.
Examples of the aromatic heterocyclic group include pyridyl, furyl, and thienyl.

The groups represented by R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Specifically, each group is as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, pentyl, hexyl, and heptyl. Linear or branched alkyl such as octyl, or cyclic alkyl such as cyclohexyl. A linear or branched alkyl group having 1 to 4 carbon atoms is preferred, and a methyl or ethyl group is more preferred.

The group represented by R ⁴ is an alkyl group, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, fluorenyl group, fluorenylamino group, oxycarbonyl group, cyano group, allyl group, or alkynyl group having 1 to 8 carbon atoms. The propyl group is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, pentyl, hexyl, and heptyl. Linear or branched alkyl such as octyl, and cyclic alkyl such as cyclohexyl. A linear or branched alkyl group having 1 to 4 carbon atoms is preferred, and a methyl or ethyl group is more preferred.
Examples of the aryl group include a phenyl group and a naphthyl group. Preferred is phenyl.
Examples of the substituted aryl group include a phenyl group having a substituent, and a naphthyl group having a substituent. Examples of the substituent of the aryl group having a substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amine group, a nitro group, a cyano group, and a carbonyl group-containing group represented by -COR ⁴¹¹ (R ⁴¹¹ is a group having 1 to 8 carbon atoms) Alkyl, aryl, alkoxy or aryloxy having 1 to 8 carbons), sulfofluorenyl, trifluoromethyl and the like. Moreover, these substituents may substitute one or two.
Examples of the aromatic heterocyclic group include pyridyl, furyl, and thienyl.
The alkoxy group is preferably a group having an alkyl group having 1 to 8 carbon atoms bonded to an oxygen atom. Oxy, tertiary butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.
Examples of the fluorenyl group include an ethenyl group, a propionyl group, and a benzamyl group.
Examples of the fluorenyl group include -CONR ⁴²¹ R ⁴²² (R ⁴²¹ and R ⁴²² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).
The oxycarbonyl group is preferably a group represented by -COOR ⁴³¹ (R ⁴³¹ is a hydrogen atom, an alkyl group having 1 to 8 carbons or an aryl group), and examples thereof include a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group. , N-butoxycarbonyl, second butoxycarbonyl, third butoxycarbonyl, n-pentyloxycarbonyl, phenoxycarbonyl, and the like. Preferable oxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl.
Examples of allyl groups include -CR ⁴⁴¹ R ⁴⁴² -CR ⁴⁴³ = CR ⁴⁴⁴ R ⁴⁴⁵ (R ⁴⁴¹ and R ⁴⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴⁴³ , R ⁴⁴⁴ , and R ⁴⁴⁵ are each independent It is a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and each substituent may be linked in a cyclic structure).
Examples of propargyl include -CR ⁴⁵¹ R ⁴⁵² -C≡CR ⁴⁵³ (R ⁴⁵¹ and R ⁴⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R ⁴⁵³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; Aryl or silicon).

Specific examples of the organic tellurium compound represented by the general formula (11) include (methyl tellurylmethyl) benzene, (methyl tellurylmethyl) naphthalene, and ethyl-2-methyl-2-methyltelluryl. -Propionate, ethyl-2-methyl-2-n-butyl telluryl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methyl telluryl- Propionate, (2-hydroxyethyl) -2-methyl-2-methyl telluryl-propionate, or (3-trimethylsilylpropargyl) -2-methyl-2-methyl All organic tellurium compounds are described in Tetrayl-propionate and the like, 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 the general formula (12) include dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, and bicyclic Propyl ditelluride, di-n-butyl ditelluride, two second butyl ditellurides, two third butyl ditellurides, dicyclobutyl di tellurides, diphenyl di tellurides, bis- ( P-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis- (p-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, Bis- (p-sulfofluorenylphenyl) ditelluride, dinaphthyl ditelluride, dipyridyl ditelluride, and the like.

The azo-based polymerization initiator may be any azo-based polymerization initiator used in general radical polymerization, and is not particularly limited. For example, 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis (2-methylbutyronitrile) (AMBN), 2,2'-azobis (2 , 4-dimethylvaleronitrile) (ADVN), 1,1'-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2'-azobisisobutyrate (MAIB), 4,4'-Azobis (4-cyanovaleric acid) (ACVA), 1,1'-Azobis (1-ethoxyl-1-phenylethane), 2, 2'-azobis (2-methylbutylamidamine), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70), 2, 2'-azobis (2-methylformamylpropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'- Azobis [2-methyl-N- (2-hydroxyethyl) propanamine], 2,2'-azobis (2,4,4-trimethylpentane), 2-cyano- 2-propylazomidine, 2,2'-azobis (N-butyl-2-methylpropanamide), or 2,2'-azobis (N-cyclohexyl-2- Methamphetamine) and the like.

In the polymerization step, a vinyl monomer and an organic tellurium compound of the general formula (11) are mixed in a container substituted with an inert gas, and azo is further mixed according to the type of the vinyl monomer to promote the reaction, control the molecular weight and molecular weight distribution. It is a polymerization initiator and / or an organic ditelluride compound of the general formula (12). In this case, examples of the inert gas include nitrogen, argon, and helium. Argon and nitrogen are preferred.

In the aforementioned (a), (b), (c), and (d), the amount of vinyl monomer used may be appropriately adjusted according to the physical properties of the target copolymer. It is preferably 5 mol to 10,000 mol based on 1 mol of the organic tellurium compound of the general formula (11).

When the organic tellurium compound of the general formula (11) and the azo-based polymerization initiator are used in combination with the aforementioned (b), the azo-based polymerization initiator is preferably 0.01 mol relative to 1 mol of the organic tellurium compound of the general formula (11). ~ 10mol.

When the organic tellurium compound of the general formula (11) and the organic ditelluride compound of the general formula (12) are used together in the above (c), 1 mol of the organic tellurium compound of the general formula (11) The telluride compound is preferably 0.01 mol to 100 mol.

When using the organic tellurium compound of the general formula (11) and the organic ditelluride compound of the general formula (12) and an azo-based polymerization initiator in the above (d), 1 mol of the organic tellurium compound of the general formula (11), The organic ditelluride compound of the general formula (12) is preferably 0.01 mol to 100 mol, and the azo-based polymerization initiator is preferably 0.01 mol to 100 mol relative to 1 mol of the organic tellurium compound of the general formula (11).

The polymerization reaction can be performed without a solvent, and the polymerization reaction can be performed by stirring the mixture using an aprotic solvent or a protic solvent generally used for radical polymerization. Examples of aprotic solvents that can be used include anisole, benzene, toluene, N, N-dimethylformamide (DMF), dimethylsulfinium (DMSO), acetone, 2-butanone (methyl Ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate or trifluoromethylbenzene, and the like. Examples of the protic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cyperidine, butyl cyperidine, 1-methoxy-2-propanol, hexafluoroisopropanol, or Diacetone alcohol and so on.

The amount of solvent to be used may be appropriately adjusted. For example, it is preferably 0.01 ml or more, more preferably 0.05 ml or more, still more preferably 0.1 ml or more, more preferably 50 ml or less, and still more preferably 10 ml or less with respect to 1 g of the vinyl monomer. , And more preferably below 1ml.

The reaction temperature and reaction time can be appropriately adjusted according to the molecular weight or molecular weight distribution of the obtained copolymer, and it is usually stirred at 0 ° C to 150 ° C for 1 minute to 100 hours. The TERP method can obtain high yield and precise molecular weight distribution even at low polymerization temperature and short polymerization time. At this time, the pressure is usually performed at normal pressure, but it may be increased or reduced.

After the polymerization reaction is completed, the solvent used and the remaining vinyl monomers are removed from the obtained reaction mixture by a general separation and purification method, so that the target copolymer can be separated.

For example, the vinyl monomers constituting the blocks are sequentially polymerized by a living radical polymerization method, thereby obtaining the block copolymer of the present invention. Specifically, the following methods can be cited:
In the case of the AB block, the polymerization method includes a step of polymerizing the vinyl monomer constituting the A block by a living radical polymerization method to polymerize the A block, and polymerizing the vinyl monomer constituting the B block after the A block is polymerized. A step of polymerizing the B block;
When it is an ABA block, the polymerization method includes a step of polymerizing one A block by polymerizing a vinyl monomer constituting one of the two A blocks by a living radical polymerization method, and polymerizing the one A block. A step of polymerizing the B block by the vinyl monomer of the B block, and a step of polymerizing the vinyl monomer constituting the other of the two A blocks after the polymerization of the B block and the step of polymerizing the other A block .

The growth terminal of the copolymer obtained from the polymerization reaction is in the form of -TeR ¹ (where R ¹ is the same as the above) derived from a tellurium compound. After the polymerization reaction is completed, it will be deactivated in the air, but tellurium atoms will remain. . Copolymers in which tellurium atoms remain at the ends may be colored or have poor thermal stability, so it is preferred to remove tellurium atoms.

The method for removing tellurium atoms can be used:
Free radical reduction method using tributylstannane or thiol compound;
Adsorption methods such as activated carbon, silica gel, activated alumina, activated clay, molecular sieve, and polymer adsorbent; ion exchange resins; methods for adsorbing metals;
Add hydrogen peroxide or peroxide such as benzamidine peroxide, or blow air or oxygen into the system to oxidatively decompose the tellurium atoms at the end of the copolymer, and wash the water or an appropriate solvent to remove the remaining tellurium compounds. Liquid-liquid extraction or solid-liquid extraction;
Removal methods such as ultrafiltration in a solution state that remove only those with a specific molecular weight or less;
These methods can be used in combination.

When the tertiary amine group of the structural unit represented by the formula (2) is quaternized, the quaternizing agent includes halogenated alkane such as methyl chloride, ethyl chloride, bromomethane, and methyl iodide; Aryl halides such as methyl iodide; diaryl sulfates such as diphenyl sulfate; dimethyl sulfate; dialkyl sulfates such as diethyl sulfate and di-n-propyl sulfate; methyl p-toluenesulfonate and p-toluenesulfonate Aromatic alkyl sulfonates, such as ethyl acetate. Among these, aralkyl halides such as benzyl chloride, benzyl bromide, and benzyl iodide, dialkyl sulfates such as dimethyl sulfate, diethyl sulfate, and di-n-propyl sulfate, and methyl p-toluenesulfonate are preferred. Aromatic sulfonic acid alkyl esters such as esters and ethyl p-toluenesulfonate are more preferably benzyl chloride, dimethyl sulfate, and methyl p-toluenesulfonate. The quaternized structure introduces an alkyl group and an aralkyl group derived from a quaternary agent. Therefore, the amount of the structural unit represented by the formula (1) can be estimated by measuring the amount of the alkyl group and the aralkyl group introduced by the quaternization.

The method of quaternizing the tertiary amine structure which is a part of the structural unit represented by formula (2) in the polymer includes a method of contacting the polymer with a quaternizing agent. Specific examples include a method of polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the formula (2), and then adding a quaternizing agent to the reaction solution and stirring it. The temperature of the reaction solution to which the quaternizing agent is added is preferably 25 ° C to 65 ° C, more preferably 55 ° C to 65 ° C, and the stirring time is preferably 1 hour to 40 hours, and more preferably 5 hours to 20 hours. When a quaternizing agent is added, the reaction liquid after polymerization is preferably diluted. The solvent to be added for dilution includes solvents that can be used in the polymerization reaction, protic solvents, and mixed solvents of the solvents used in the polymerization reaction and the protic solvent, and may be appropriately selected depending on the solubility of the target block copolymer. The protic solvent is more preferably methanol.

(b) Aromatic compound The dispersant composition of the present invention contains (b) at least one selected from the group consisting of an aromatic dicarboxylic acid sulfonium imine, an acidic group-containing aromatic compound, and a phenolic hydroxyl group-containing aromatic compound. An aromatic compound. The dispersant composition contains (b) an aromatic compound to improve dispersibility. (b) The aromatic compound may be blended with only one kind or in combination with two or more kinds.

The aromatic dicarboxylic acid sulfonium imine has an aromatic ring and a sulfonium imine group (-C (= O) NHC (= O)-) directly bonded to the aromatic ring in the molecule. The two ends of the fluorene imino group may be bonded to one aromatic ring or may be respectively bonded to different aromatic rings, but it is preferred that the two terminals are bonded to one aromatic ring. The aromatic dicarboxylic acid sulfonium imine is preferably a compound represented by the general formula (3).

[Chemical Formula 8]
[In the general formula (3), the ring A represents an aromatic ring which may have a substituent. A

In the general formula (3), the aromatic ring constituting the ring A has an aromatic ring structure. The aromatic ring includes a monocyclic ring and a condensed ring. The aforementioned monocyclic ring is preferably a 5- or 6-membered ring, and is preferably a benzene ring, a furan ring, a thiophene ring, or a pyrrole ring. The aforementioned condensed ring is preferably a 2 to 5 condensed ring, and preferably a naphthalene ring, an anthracene ring, a phenanthrene ring, or an indole ring. Among these, it is preferred that the atoms constituting the ring structure in the ring structure contain no heteroatoms. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.

Specific examples of the aromatic dicarboxylic acid sulfonium imine include the following compounds.

[Chemical Formula 9]

The acidic group-containing aromatic compound has an aromatic ring in the molecule and an acidic group directly bonded to the aromatic ring. Examples of the acidic group include a carboxyl group (-COOH), a sulfonic acid group (-SO ₃ H), a phosphate group (-OPO ₃ H ₂ ), a phosphonic acid group (-PO ₃ H ₂ ), and a phosphonic acid group (-PO ₂ H ₂ ). The number of acidic groups may be one or plural. Moreover, when having a plurality of acidic groups, it may have a plurality of acidic groups. The acidic group-containing aromatic compound is preferably a compound represented by the general formula (4) (that is, an aromatic carboxylic acid, an aromatic sulfonic acid, and an aromatic phosphonic acid).

[Chemical Formula 10]
[In Formula (4), ring A represents an aromatic ring which may have a substituent. A

In the general formula (4), the aromatic ring constituting the ring A has an aromatic ring structure. The aromatic ring includes a monocyclic ring and a condensed ring. The aforementioned monocyclic ring is preferably a 5- or 6-membered ring, and is preferably a benzene ring, a furan ring, a thiophene ring, or a pyrrole ring. The aforementioned condensed ring is preferably a 2 to 5 condensed ring, and preferably a naphthalene ring, an anthracene ring, a phenanthrene ring, or an indole ring. Among these, it is preferred that the atoms constituting the ring structure in the ring structure contain no heteroatoms. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.

Specific examples of the aromatic carboxylic acid include the following compounds.

[Chemical Formula 11]

Specific examples of the aromatic sulfonic acid include the following compounds.

[Chemical Formula 12]

Specific examples of the aromatic phosphonic acid include the following compounds.

[Chemical Formula 13]

The phenolic hydroxyl-containing aromatic compound has an aromatic ring in the molecule and a hydroxyl group directly bonded to the aromatic ring. The number of hydroxyl groups may be one or plural. The phenolic hydroxyl group-containing aromatic compound is preferably a compound represented by the general formula (5).

[Chemical Formula 14]
[In the general formula (5), the ring A represents an aromatic ring which may have a substituent. A

In the general formula (5), the aromatic ring constituting the ring A has an aromatic ring structure. The aromatic ring includes a monocyclic ring and a condensed ring. The aforementioned monocyclic ring is preferably a 5- or 6-membered ring, and is preferably a benzene ring, a furan ring, a thiophene ring, or a pyrrole ring. The aforementioned condensed ring is preferably a 2 to 5 condensed ring, and preferably a naphthalene ring, an anthracene ring, a phenanthrene ring, an indole ring, a coumarin ring, or an xanthracene ring. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.

Specific examples of the phenolic hydroxyl group-containing aromatic compound include the following compounds.

[Chemical Formula 15]

(c) Tertiary amine compound The dispersant composition contains (c) a tertiary amine compound. The (c) tertiary amine compound has a tertiary amine structure in the molecule. The dispersant composition contains (c) a tertiary amine compound, whereby a salt can be formed with the aforementioned (b) aromatic compound. (c) The tertiary amine compound may be blended with only one type or in combination with two or more types.

The tertiary amine compound (c) is preferably a compound represented by the general formula (6) or a compound represented by the general formula (7), and more preferably a compound represented by the general formula (7). By compounding the compound represented by the general formula (7) as the tertiary amine compound (c), the brightness of the coating film formed by the coloring composition can be improved.

[Chemical Formula 16]
[In the general formula (6), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. R ⁶² and R ⁶³ may be bonded to each other to form a ring structure. A

Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R ⁶¹ , R ⁶² and R ⁶³ include a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Aralkyl group having 7 to 10 carbon atoms, and alkylaryl group having 7 to 10 carbon atoms.

Examples of the compound represented by the general formula (6) include trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, and N-ethyl Aliphatic amines such as dipentylamine; aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline; N, N-dimethyl-cyclohexylamine, N, N-diethyl- Alicyclic amines such as cyclohexylamine.

[Chemical Formula 17]
[In the general formula (7), R ⁷¹ represents a divalent hydrocarbon group having 2 to 6 carbons which may have a substituent, and R ⁷² and R ⁷³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbons which may have a substituent. R ⁷² and R ⁷³ may be bonded to each other to form a ring structure. A

Examples of the hydrocarbon group having 2 to 6 carbon atoms represented by R ⁷¹ include an alkylene group having 2 to 6 carbon atoms. Examples of the substituent having a divalent hydrocarbon group having 2 to 6 carbon atoms represented by R ⁷¹ include a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms. Group, aralkyl group having 7 to 10 carbon atoms, and alkylaryl group having 7 to 10 carbon atoms.

Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R ⁷² and R ⁷³ include a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and carbon number. Aryl groups of 7 to 10 and alkyl aryl groups of 7 to 10 carbon atoms.

The compound represented by the general formula (7) is preferably a cyclic fluorene compound represented by the general formula (8).

[Chemical Formula 18]
[In the general formula (8), R ^{80 to} R ⁸⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. n is an integer from 1 to 4. m is an integer from 1 to 4. A

Specific examples of the compound represented by the general formula (8) include the following compounds.

[Chemical Formula 19]

The dispersant composition preferably contains a solvent. The solvent may be an organic solvent, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether. Ethyl ether, propylene glycol mono-n-butyl ether, propylene glycol third butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monoethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl Glycol monoalkyl ethers such as alkyl ethers; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethylene glycol Glycol dialkyl ethers such as propyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methyl acetate Oxybutane , 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether Acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate Glycol alkyl ether acetates such as esters; glycol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanol diacetate; cyclic Alkyl acetates such as hexanol acetate; pentyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, dipentyl ether, ethyl isobutyl Ethers such as ether and dihexyl ether; acetone, methyl ethyl ketone, methyl pentanone, methyl isoacetone, methyl isopentanone, diisoacetone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone , Ketones such as ethylpentanone, methylbutanone, methylhexanone, methylnonanone, methoxymethylpentanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol , Propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, Mono- or polyhydric alcohols such as methoxymethylpentanol, glycerol, benzyl alcohol; fats such as n-pentane, n-octane, sesquibutene, n-hexane, hexene, isoprene, dipentene, dodecane, etc. Hydrocarbons; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate , Ethyl formate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, butyl acetate Isobutyl ester, methyl isobutyrate, ethyl octoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxy Chain or cyclic esters such as methyl propionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; acetonitrile and benzoyl Nitriles such as nitrile. The organic solvent contained in the dispersant composition may be only one kind or plural kinds.

The dispersant composition can be prepared by mixing (a) a block copolymer, (b) an aromatic compound, (c) a tertiary amine compound, and a solvent as needed. In addition, it is considered that (b) an aromatic compound and (c) a tertiary amine compound are reacted to form an organic salt after mixing, so a mixture of (b) an aromatic compound and (c) a tertiary amine compound may be mixed beforehand (e.g. ) And (a) a salt composed of an aromatic compound and a tertiary amine compound, and (a) a block copolymer. The raw materials can be mixed using, for example, a paint disperser, a bead mill, a ball mill, a dissolver, a kneader, and the like. When preparing the dispersant composition, the mixing temperature is preferably 50 ° C or higher, more preferably 55 ° C or higher, still more preferably 60 ° C or higher, more preferably 75 ° C or lower, more preferably 70 ° C or lower, and even more preferably 65 ° C. Below ℃.

In the dispersant composition, the molar ratio of the quaternary ammonium salt group in the (a) block copolymer to the (b) aromatic compound (the quaternary ammonium salt group in (b) / (a)) It is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.0 or more, more preferably 1.2 or less, even more preferably 1.1 or less, and still more preferably 1.05 or less.

In the dispersant composition, the molar ratio of the quaternary ammonium salt group in the (a) block copolymer to the (c) tertiary amine compound (the quaternary ammonium salt group in (c) / (a) ) Is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.0 or more, more preferably 1.2 or less, even more preferably 1.1 or less, and still more preferably 1.05 or less.

In the dispersant composition, the molar ratio of the acidic groups in the (a) block copolymer and the (b) aromatic compound to the (c) tertiary amine compound ((c) / ((a) The acidic group + (b)) is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, more preferably 1.0 or less, more preferably 0.9 or less, and still more preferably 0.8 or less.

In the dispersant composition, the molar ratio ((b) / (c)) of the (b) aromatic compound to the (c) tertiary amine compound is preferably 0.9 or more, more preferably 0.95 or more, and more It is preferably 1.0 or more, preferably 1.1 or less, more preferably 1.05 or less, and still more preferably 1.02 or less.

When the total of the (a) block copolymer, (b) aromatic compound, and (c) tertiary amine compound is 100 parts by mass, the amount of the solvent used is preferably 50 parts by mass or more, and more preferably 100 parts by mass The above, and more preferably 200 parts by mass or more, preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and still more preferably 250 parts by mass or less.

The acid value of the solid content of the dispersant composition is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, more preferably 70 mgKOH / g or less, and even more preferably 65 mgKOH / g. Hereinafter, it is more preferably 60 mgKOH / g or less. If the acid value is 5 mgKOH / g or more, the solubility in alkali is high, and the rate of dissolution in alkali is faster. If it is 70 mgKOH / g or less, the viscosity of the coloring composition will not be too high, and the coating property of the photoresist composition will be better. . Here, the solid content is a component other than a solvent.

The amine value of the solid content of the dispersant composition is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, still more preferably 50 mgKOH / g or more, more preferably 150 mgKOH / g or less, and even more preferably 120 mgKOH / g Hereinafter, it is more preferably 95 mgKOH / g or less. When the amine value is 10 mgKOH / g or more, the stability of the viscosity of the coloring composition over time is further improved, and when it is 150 mgKOH / g or less, the viscosity increase of the coloring composition can be suppressed.

(Coloring composition)
The coloring composition of this invention contains the said dispersant composition, a coloring material, a dispersing medium, and a binder resin.

(Coloring material)
The kind of the coloring material can be appropriately selected depending on the application, and examples thereof include pigments and dyes. From the viewpoint of light resistance and heat resistance, the coloring composition preferably contains a pigment as a coloring material. The pigment may be any one of an organic pigment and an inorganic pigment, but an organic pigment mainly containing an organic compound is particularly preferred. Examples of the pigment include red pigments, yellow pigments, orange pigments, blue pigments, green pigments, and purple pigments. Examples of the pigment structure include azo pigments such as monoazo pigments, diazo pigments, and condensed diazo pigments; diketopyrrolopyrrole pigments; phthalocyanin pigments; isoindolinone pigments; Polycyclics such as indolinoline pigments, quinacridone-based pigments, indigo-based pigments, thioindigo-based pigments, quinoline yellow-based pigments, dioxazine-based pigments, anthraquinone-based pigments, fluorene-based pigments, and ringtone-based pigments Department of pigments and so on. The pigment contained in the coloring composition may be only one type, or may be plural types for the purpose of adjusting chromaticity and the like.

Specific examples of the pigment include CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, 146, 149, 166, 168, 177, 178, 179, 187, 200, 202, 208, 210, 215, 224, 242, 254, 255, 264, 269 and other red pigments; CI Pigment Yellow 1, 3, 5, 6, 14, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 93, 97, 98, 104, 108, 110, 138, 139, 147, 150, 151, 154, 155, 166, 167, 168, 170, 180, 185, 188, 193, 194, 213 and other yellow pigments; CI Pigment Orange 36, 38, 43 and other orange pigments; CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 22, 60 and other blue pigments; CI Pigment Green 7, 36, 58, 59, 62, 63, aluminum phthalocyanin, polyhalophthalocyanin, aluminum Phthalocyanin hydroxide, diphenoxyphosphinooxyaluminum phthalocyanin, diphenylphosphinooxyaluminum phthalocyanin, polyhalogenated diphenoxyphosphinooxyaluminum phthalocyanin, polyhalogenated diphenylphosphine Green pigments such as oxyaluminum phthalocyanin; purple pigments such as CI Pigment Violet 23, 32, 50 . The pigment is preferably CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 269, CI Pigment Blue 15, CI Pigment Blue 15: 2, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 16, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, etc.

In the present invention, the dispersant composition is preferably used together with a coloring material containing a phthalocyanin pigment, and more specifically, it is preferably used with Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, and Pigment Blue. 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 17, Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, CI Pigment Green 63, Aluminum Phthalocyanin, polyaluminum phthalocyanin, aluminum phthalocyanin hydroxide, diphenoxyphosphinooxyaluminum phthalocyanine, diphenylphosphinooxyaluminum phthalocyanin, polyhalogenated diphenoxyphosphino Oxyaluminum phthalocyanin, polyhalogenated diphenylphosphinooxyaluminum phthalocyanin and other coloring materials are used together. More preferably, it is used together with a coloring material containing a polyhalogenated phthalocyanin-based pigment.

When using the coloring composition of the present invention to form a light-shielding material such as a black matrix of a color filter, a black pigment can be used. The black pigment may be used alone, and the red pigment, the green pigment, the blue pigment, and the like may be mixed and used. Examples of the black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferred from the viewpoints of light shielding rate and image characteristics.

The number average particle diameter of the coloring material can be appropriately selected depending on the application, and is not particularly limited. From the viewpoint of high transparency and high contrast, the coloring composition preferably contains a coloring material having a number average particle diameter of 10 to 150 nm.

The coloring material may contain a pigment derivative as a dispersing aid. In order to bond and adsorb the tertiary amine group and the quaternary ammonium salt group in the resin-based dispersant, the pigment derivative preferably contains an acidic pigment derivative having an acidic group. The pigment derivative is one in which an acidic functional group is introduced into a pigment skeleton. The pigment skeleton is preferably a skeleton that is the same as or similar to the coloring material constituting the coloring composition, or a skeleton that is the same or similar to the compound of the coloring material raw material. Specific examples of the pigment skeleton include an azo pigment skeleton, a phthalocyanin pigment skeleton, an anthraquinone pigment skeleton, a triazine pigment skeleton, an acridine pigment skeleton, and a fluorene pigment skeleton. The acidic group introduced into the pigment skeleton is preferably a carboxyl group, a phosphate group, or a sulfonic acid group. Moreover, in view of the convenience of synthesis and the strength of acidity, a sulfonic acid group is preferred. The acidic group may be directly bonded to the pigment skeleton, or may be bonded to the pigment skeleton through a hydrocarbon group such as an alkyl group or an aryl group; an ester, ether, sulfonamide, or urethane bond. The amount of the pigment derivative used is not particularly limited, and for example, it is preferably 4 to 17 parts by mass based on 100 parts by mass of the coloring material.

From the viewpoint of brightness, the upper limit value of the coloring material content in the coloring composition is usually 80% by mass, preferably 75% by mass, and more preferably 70% by mass of the total solid content of the coloring composition. The lower limit value of the coloring material content in the coloring composition is usually 10% by mass, preferably 30% by mass, and more preferably 50% by mass of the total solid content of the coloring composition. Here, the solid content is a component other than the dispersion medium described later.

The content of the (a) block copolymer is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and more preferably 100 to 100 parts by mass of the coloring material in the coloring composition. It is preferably 10 parts by mass to 80 parts by mass.

(Dispersed media)
In the aforementioned coloring composition, as long as the dispersing medium can disperse or dissolve other components constituting the coloring composition, does not react with these components, and has moderate volatility, it can be appropriately selected and used. For example, conventionally known organic solvents can be used, and those exemplified for the solvent of the dispersant composition can be used. From the viewpoints of dispersibility of a coloring material and the like, dispersant solubility, coating property of a coloring composition, and the like, the organic solvent is preferably a glycol alkyl ether acetate, a monohydric or polyhydric alcohol. The solvent contained in the coloring composition may be only one kind or plural kinds.

When a pixel of a color filter is formed by photolithography, the boiling point of the dispersing medium is preferably 100 ° C to 200 ° C (under a pressure of 1013.25 hPa. The following points are the same regarding the boiling point), and more preferably 120 ° C to 170 ° C. . In view of good balance between coatability and surface tension, and high solubility of constituent components in the colored composition, glycol alkyl ether acetates are preferred among the dispersing media. Glycol alkyl ether acetates can be used alone or in combination with other dispersion media. In this case, a dispersion medium having a boiling point of 150 ° C. or higher is preferably used in combination. By using such a high-boiling-point dispersing medium in combination, the coloring composition can be prevented from being dried easily, and the relationship between the coloring composition can be prevented from being destroyed by rapid drying. The content ratio of the dispersion medium having a boiling point of 150 ° C. or higher is preferably 3% to 50% by mass relative to 100% by mass of the entire dispersion medium. When the content ratio is 3% by mass or more, it is possible to suppress the occurrence of foreign matter defects such as precipitation and solidification of colored materials at the tip of the slit nozzle. If it is 50% by mass or less, the drying speed of the colored composition is slowed, and the problem of prolonged drying time and the occurrence of pre-baking pin marks during the production of a color filter described later can be suppressed. Further, the dispersion medium having a boiling point of 150 ° C or higher may be a glycol alkyl ether acetate, and in this case, it is not necessary to include a dispersion medium having a boiling point of 150 ° C or higher.

When the pixels of the color filter are formed by the inkjet method, the boiling point of the dispersion medium is preferably 130 ° C to 300 ° C, and more preferably 150 ° C to 280 ° C. By setting the boiling point to 130 ° C or higher, the uniformity of the obtained coating film can be made good. In addition, by setting the boiling point to 300 ° C or lower, the residual solvent in the coating film after thermal firing can be reduced, quality defects can be suppressed, and the drying time can be prolonged. From the viewpoint of the uniformity of the obtained coating film, the vapor pressure of the dispersing medium can generally be 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less.

In addition, when the color filter is manufactured by the inkjet method, the printing ink emitted from the nozzle is only pL to tens of pL, which is very fine. Therefore, the dispersion medium is evaporated around the nozzle mouth or before it is attached to the pixel library. The tendency of ink to condense and dry. In order to avoid this situation, the boiling point of the dispersion medium is preferably high, and specifically, it is preferable that the dispersion medium contains a dispersion medium having a boiling point of 180 ° C or higher. More preferably, it contains a dispersion medium having a boiling point of 200 ° C or more, and particularly preferably contains a dispersion medium having a boiling point of 220 ° C or more. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more with respect to 100% by mass of the entire dispersion medium contained in the coloring composition. When it is equal to or more than the aforementioned lower limit value, there is a tendency that the effect of preventing evaporation of the solvent from the liquid droplets can be sufficiently exerted.

The content of the dispersion medium in the coloring composition can be appropriately adjusted, and is not particularly limited. In the coloring composition, the upper limit of the content of the dispersion medium is usually 99% by mass. Moreover, considering the viscosity suitable for coating a coloring composition, the lower limit of the content of the dispersing medium in the coloring composition is usually 70% by mass, preferably 75% by mass. The dispersion medium can be used as a solvent for dissolving and removing a precipitate formed by the colored composition.

(Binder resin)
The coloring composition of this invention contains a binder resin (except the said (a) block copolymer). This can improve the alkali developability of the coloring composition or the adhesion to the substrate. Such a binder resin is not particularly limited, and a resin having an acidic group such as a carboxyl group or a phenolic hydroxyl group is preferred. The aforementioned binder resin may be, for example, an unsaturated monobasic acid added to at least a part of the epoxy group in the copolymer of the epoxy group-containing (meth) acrylate and other radical polymerizable monomers. The resin formed, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups produced in the addition reaction; a linear alkali-soluble resin containing a carboxyl group in the main chain; Resin of oxo unsaturated compound; (meth) acrylic resin; epoxy (meth) acrylate resin with carboxyl group, etc. These can be used alone or in combination of two or more.

The aforementioned binder resin is preferably: a random copolymer containing a structural unit derived from a carboxyl group-containing vinyl monomer, a structural unit derived from a (meth) acrylate, and styrene; (Meth) acrylfluorene-based synthetic resin; and random copolymers containing a structural unit derived from a carboxyl-containing vinyl monomer and a structural unit derived from a (meth) acrylate. The carboxyl group-containing vinyl monomer is preferably (meth) acrylic acid. Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and benzyl (meth) acrylate , Phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isoamyl (meth) acrylate, adamantane (meth) acrylate, tricyclodecyl (meth) acrylate, ( 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, glycidyl (meth) acrylate, ( 3,4-epoxycyclohexyl methyl methacrylate, tetrahydrofurfuryl (meth) acrylate, and the like.

In the aforementioned binder resin, the total content of the structural unit derived from the carboxyl group-containing vinyl monomer and the structural unit derived from (meth) acrylate is preferably 50% by mass or more, and more preferably 60% by mass. The above is more preferably 70% by mass or more. In the aforementioned binder resin, the content rate of the structure derived from a carboxyl group-containing vinyl monomer is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. It is 90% by mass or less, and more preferably 70% by mass or less.

Among these, a random copolymer of a carboxyl group-containing vinyl monomer and a (meth) acrylate is preferable. Specific examples of such copolymers include random copolymers of (meth) acrylic acid and butyl (meth) acrylate, random copolymers of (meth) acrylic acid and benzyl (meth) acrylate, and (meth) acrylic acid. Random copolymers with butyl (meth) acrylate and benzyl (meth) acrylate. From the viewpoint of the affinity between the binder resin and the coloring material, the binder resin is particularly preferably a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate.

In the copolymer of a carboxyl group-containing vinyl monomer and a (meth) acrylic acid ester, the content of the (meth) acrylic acid in the total monomer component is usually 5 to 90% by mass, preferably 10 to 70% by mass. Mass%, more preferably 20% to 70% by mass.

The aforementioned binder resin may have a free-radically polymerizable carbon-carbon double bond in a side chain. By having a double bond in the side chain, the light-hardening property of the colored composition of the present invention is improved, so that the resolution and adhesion can be further improved. Methods for introducing a radically polymerizable carbon-carbon double bond into a side chain include, for example, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, ortho (or meta) Or a method of reacting a compound such as vinyl benzyl glycidyl ether with the acidic group of the aforementioned binder resin.

The Mw of the binder resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 20,000. If the Mw of the binder resin is 3,000 or more, the heat resistance and film strength of the colored layer formed by the coloring composition are good, and if the Mw is 100,000 or less, the alkali developability of the coating film is better.

The acid value of the binder resin is preferably 20 mgKOH / g to 170 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and still more preferably 90 mgKOH / g to 150 mgKOH / g. When the acid value of the binder resin is 20 mgKOH / g or more, the alkali developability when the colored composition forms a colored layer is better, and when the acid value is 170 mgKOH / g or less, the heat resistance is good.

The binder resin contained in the coloring composition may be only one kind or plural kinds. In the coloring composition, the content of the binder resin is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 20 to 80 parts by mass based on 100 parts by mass of the coloring material. Serving.

(Crosslinking agent)
The coloring composition may contain a crosslinking agent. The crosslinking agent is a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an ethylene oxide group, an oxetanyl group, and an N-alkoxymethylamino group. The crosslinking agent is preferably a compound having two or more (meth) acrylfluorenyl groups or a compound having two or more N-alkoxymethylamino groups. The aforementioned crosslinking agents can be used alone or in combination of two or more.

Specific examples of the compound having two or more (meth) acrylfluorenyl groups include polyfunctional (meth) acrylates and caprolactones obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid. Functional (meth) acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylic acid obtained by reacting (hydroxy) (meth) acrylate with polyfunctional isocyanate Esters, polyfunctional (meth) acrylates having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.

Examples of the aforementioned aliphatic polyhydroxy compounds include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerol, trimethylolpropane, neopentyl tetraol, and dipentaerythritol. Trivalent or higher aliphatic polyhydroxy compounds. Examples of the (meth) acrylate having a hydroxyl group include, for example, 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentaerythritol tri (meth) acrylate, di Neopentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, glycerol di (meth) acrylate, and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. Examples of the acid anhydride include dibasic anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; pyromite anhydride, biphenyltetracarboxylic acid di Tetracarboxylic dianhydride such as anhydride, diphenyl ketone tetracarboxylic dianhydride, and the like.

In the coloring composition of the present invention, the content of the crosslinking agent is preferably 10 parts by mass to 1,000 parts by mass, and more preferably 20 parts by mass to 500 parts by mass based on 100 parts by mass of the coloring material. If the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, when the crosslinking amount is too large, the colored composition of the present invention tends to have reduced alkali developability, and tends to cause dirty plates, film residues, and the like on the substrate of the unexposed portion or the light-shielding layer.

(Photopolymerization initiator)
The coloring composition preferably contains a photopolymerization initiator. This makes it possible to impart a radiation-sensitive property to the coloring composition. The photopolymerization initiator is a compound that generates active species capable of starting polymerization of a crosslinking agent upon exposure to radiation such as visible light, ultraviolet rays, far infrared rays, electron rays, and X-rays.

Examples of the photopolymerization initiator include thioxanthone-based compounds, acetophenone-based compounds, diimidazole-based compounds, triazine-based compounds, O-fluorenyl oxime-based compounds, onium salt-based compounds, benzoin-based compounds, and diphenyl. Ketone-based compound, α-diketone-based compound, polynuclear quinone-based compound, diazonium-based compound, sulfonium iminosulfonate-based compound, and the like. The photopolymerization initiator can be used alone or in combination of two or more.

In the coloring composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, and more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the crosslinking agent. At this time, if the content of the photopolymerization initiator is too small, exposure hardening may be insufficient. On the other hand, if the content of the photopolymerization initiator is too large, the colored layer may tend to fall off the substrate during development.

(Other compounding agents)
To the extent that the preferred physical properties of the present invention are not impaired, the coloring composition may be blended with other blending agents in addition to the aforementioned blending agents. Other compounding agents include sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, plasticizers, organic carboxylic acid compounds, organic Carboxylic anhydride, pH adjuster, antioxidants other than the aforementioned phenol-based antioxidants, ultraviolet absorbers, light stabilizers, preservatives, mildew inhibitors, aggregation inhibitors, adhesion improvers, development improvers, storage stabilizers, etc. .

Examples of the sensitizing dye include 4,4'-dimethylaminodiphenyl ketone, 4,4'-diethylaminodiphenyl ketone, 2-aminodiphenyl ketone, and 4-aminodiphenyl Ketone, 4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone, 3,4-diaminodiphenyl ketone, 2- (p-dimethylaminophenyl) ) Benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (p-dioxane Methylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Phenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole , 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-diethyl (Methylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine and the like.

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

Examples of nonionic surfactants include fluorine surfactants (1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2 -Tetrafluorooctylhexyl ether, octaethylene glycol bis (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol bis (1,1,2,2,3,3-hexafluoropentane) Propyl ether, octapropylene glycol bis (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol bis (1,1,2,2,3,3-hexafluoropentyl) ether, perfluorododecyl (Sodium alkyl sulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc.) Polysiloxane surfactants, polyoxyethylene surfactants (polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkane Esters, polyoxyethylene fatty acid esters, glycerol fatty acid esters, polyoxyethylene glyceryl fatty acid esters, neopentyl tetraol fatty acid esters, polyoxyethylene neopentyl alcohol fatty acid esters, sorbitan fatty acid esters, poly Oxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, etc.).

Examples of the anionic surfactant include alkyl sulfonates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, and alkyl groups. Sulfate esters, higher alcohol sulfates, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate salts, poly Oxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special polymer surfactants, etc.
Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.
Examples of the amphoteric surfactant include betaine compounds, imidazolium salts, imidazolines, and amino acids.

Examples of the plasticizer include dioctyl phthalate, di (dodecyl) phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, and triphosphate Tolyl ester, dioctyl adipate, dibutyl sebacate, triethylfluorinated glycerol and the like.

Examples of the organic carboxylic acid compound include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, hexanoic acid, glycolic acid, acrylic acid, and methacrylic acid, oxalic acid, malonic acid, and succinic acid. , Glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, malonic acid, ornic acid, benzoin Carboxylic acids such as acids and phthalic acids directly bonded to a phenyl group and carboxylic acids bonded to a carboxyl group through a carbon bond.

Examples of the organic carboxylic anhydride include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2- Cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromelite anhydride, naphthalenedicarboxylic anhydride, and the like.

> Manufacturing method of coloring composition and color filter>
A dispersant composition, a coloring material, a dispersing medium, a binder resin, and a crosslinking agent, a photopolymerization initiator, and other additives as necessary may be mixed to prepare a coloring composition. In addition, (a) a block copolymer, (b) an aromatic compound, (c) a tertiary amine compound, a coloring material, a dispersing medium, a binder resin, and other components as necessary, thereby preparing a coloring composition. . For mixing, for example, a mixing and dispersing machine such as a paint mixer, a bead mill, a ball mill, a dissolver, and a kneader can be used. The colored composition is preferably filtered after mixing. Other additives include, for example, a pH adjuster, an antioxidant, an ultraviolet absorber, a light stabilizer, a preservative, a mold inhibitor, a surfactant, an aggregation inhibitor, and the like.

Since the said coloring composition has alkaline developability, it is suitable for use as a color filter.

The color filter of the present invention includes a coloring layer formed using the coloring composition. The method for manufacturing the color filter includes, for example, the following method. First, heat curing is performed on thermoplastic resin sheets such as polyester resins, polyolefin resins, polycarbonate resins, polymethyl methacrylate resins, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic resins. After applying the colored composition of the present invention in which a red pigment is dispersed on a transparent substrate such as a flexible resin sheet or various glasses, a pre-bake is performed to evaporate the solvent (dispersion medium) to form a coating film. Then, the coating film is exposed through a photomask, and then developed using an alkaline developer (aqueous solution containing an organic solvent or a surfactant and a basic compound) to dissolve and remove unexposed portions of the coating film. Thereafter, post-baking is performed, thereby forming a pixel array in which a red pixel pattern is arranged in a specific arrangement. Then, using the green coloring composition or the blue coloring composition, coating, pre-baking, exposing, developing, and post-baking of each coloring composition are performed in the same manner as described above, and the green pixel array and the blue pixel array are sequentially formed on the same On the substrate. As a result, color filters of three primary color pixel arrays of red, green and blue are arranged on the substrate. However, the order of forming the pixels of each color in the present invention is not limited to the above.

When the colored composition is coated on the substrate, a suitable coating method such as a spray method, a roll coating method, a spin coating method, a slot die coating method, or a bar coating method may be adopted, and a spin coating method or a slit is particularly preferred. Die coating method.
After forming a protective film on the pixel pattern thus obtained as needed, a transparent conductive film (ITO, etc.) is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to become a color filter. In addition, a black matrix may be provided on a transparent substrate used for forming the three primary color pixel arrays of red, green, and blue.

The color filter of the present invention has high dimensional accuracy and the like, and is suitable for use in color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like.
The coloring composition has low viscosity and excellent brightness of the coating film (coloring body) formed by the coloring composition. Therefore, it is suitable for use as a coloring column spacer. The coloring column spacer is supported on a TFT substrate sandwiching a liquid crystal layer and Color filter substrate. For example, the composition of high optical density (Optical Depth: OD) described in Unexamined-Japanese-Patent No. 2015-191234 is mentioned.
(Example)

The present invention will be further described in detail below based on specific examples. The present invention is not limited to the following examples, and appropriate changes can be made without changing the gist thereof. In addition, the polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI), amine value and acid value of the dispersant and binder resin, and the viscosity and brightness of the colored composition were evaluated by the following methods.

The abbreviations refer to the following.
BTEE: ethyl-2-methyl-2-n-butyl telluryl-propionate.
DBDT: dibutyl ditelluride.
AIBN: 2,2'-azobis (isobutyronitrile).
MMA: methyl methacrylate.
BMA: butyl methacrylate.
EHMA: 2-ethylhexyl methacrylate.
BzMA: benzyl methacrylate.
M4EGM: methoxy polyethylene glycol monomethacrylate (trade name: BLEMMER PME-200, manufactured by Nippon Oil Corporation).
DMAEMA: dimethylaminoethyl methacrylate.
BzCl: benzyl chloride.
MAA: methacrylic acid.
PI: phthalimide.
2-NA: 2-naphthoic acid.
2-NAOH: 2-naphthol.
7-HC: 7-hydroxycoumarin.
4-MU: 4-methylumbelliferone.
DBU: diazabicycloundecene.
DIPEA: diisopropylethylamine.
TEA: triethylamine.
PIDBU: phthalimide diazabicycloundecene.
PMA: propylene glycol monomethyl ether acetate.
MP: 1-methoxy-2-propanol.

(Polymerization rate)
¹ H-NMR (solvent: deuterated chloroform, internal standard: tetramethylsilane) was measured using a nuclear magnetic resonance (NMR) measurement device (Bruker's model: AVANCE500 (frequency 500 MHz)). From the obtained NMR spectrum, the peak integral ratio of the vinyl group derived from the monomer and the ester side chain derived from the polymer was calculated, and the polymerization rate of the monomer was calculated.

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))
It was determined by gel permeation chromatography (GPC) using high-speed liquid chromatography (TOSOH type: HLC8320). One column is SHODEX KF-603 (Φ6.0mm × 150mm) (manufactured by SHODEX). The mobile phase uses 30mmol / L lithium bromide-30mmol / L acetic acid-N-methylpyrrolidone. The detector uses differential refractive index detection. Device. The measurement conditions were a column temperature of 40 ° C., a sample concentration of 20 mg / mL, a sample injection amount of 10 μL, and a flow rate of 0.2 mL / min. Using polystyrene (molecular weight 427,000, 190,000, 96,400, 37,400, 10,200, 2,630, 906) as a reference material, a calibration curve (calibration curve) was prepared, and the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured. From these measured values, a molecular weight distribution (PDI = Mw / Mn) was calculated.

(Amine value)
The amine value is expressed by the mass of potassium hydroxide (KOH) equivalent to 1 g of the basic component of the solid content. The measurement sample was dissolved in tetrahydrofuran, and the obtained solution was neutralized and titrated with a 0.1 mol / L hydrochloric acid / 2-propanol solution using a potential difference titration device (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). The titration endpoint of the titration pH curve is used as the endpoint of the titration, and the amine value (B) is calculated by the following formula.
B = 56.11 × Vs × 0.1 × f / w.
B: Amine value (mgKOH / g).
Vs: 0.1 mol / L hydrochloric acid / 2-propanol solution (mL) required for titration.
f: the potency of 0.1 mol / L hydrochloric acid / 2-propanol solution.
w: measurement sample mass (g) (solid content conversion).

(Acid value)
The acid value is expressed by the mass of potassium hydroxide required to neutralize 1 g of the acid component of the solid content. The measurement sample was dissolved in tetrahydrofuran, and a few drops of a phenolphthalein ethanol solution as an indicator were added dropwise, and the solution was neutralized and titrated with a 0.1 mol / L potassium hydroxide / ethanol solution. The acid value (A) is calculated by the following formula.
A = 56.11 × Vs × 0.1 × f / w.
A: Acid value (mgKOH / g).
Vs: 0.1 mol / L potassium hydroxide / ethanol solution (mL) required for titration.
f: the potency of 0.1 mol / L potassium hydroxide / ethanol solution.
w: measurement sample mass (g) (solid content conversion).

(Viscosity)
Using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.), a tapered rotor (1 ° 34 '× R24) was used, and the viscosity was measured at 25 ° C at a rotor speed of 60 rpm.
After the colored composition was prepared and stored at 25 ° C for 2 hours, the viscosity was measured. When the viscosity is less than 10 mPa ･ s, the evaluation is “A”, and when the viscosity is 10 mPa ･ s or more, the evaluation is “B”.

(Brightness)
A colored composition was applied to a glass plate, and after drying, a heat treatment was performed at 230 ° C. for 30 minutes, thereby forming a coating film and producing a colored glass. The colored glass plate was set on a spectrophotometer (trade name: CM-3700d, manufactured by KONICA MINOLTA SENSING Co., Ltd.), and the transmission chromaticity of the XYZ coordinate axis in the C light source was measured. The Y value at this time is used as the luminance (Y). In Table 2, regarding the brightness, the colored composition Nos. 1 to 8 were evaluated based on the brightness of the colored glass plate using the colored composition No. 8, and the difference between the measured value and the reference value (measured value-reference value) was 0.4 or more is "A", the difference is more than 0 and less than 0.4 is "B", and the difference is 0 is "C". The colored composition Nos. 9 to 11 were evaluated based on the brightness of the colored glass plate using the colored composition No. 11, and the difference between the measured value and the reference value (measured value-reference value) was more than 0 and less than 0.2 is "A" and the difference is 0 is "B".

> Manufacturing block copolymers>
In a flask equipped with an argon introduction tube and a stirrer, add MMA 46.1g, BMA 22.2g, EHMA 20.9g, BzMA 15.4g, M4EGM 8.1g, MAA 8.1g, AIBN 0.82g, PMA 80.5g, replace with argon and add BTEE 7.49g, DBDT 4.61g, reacted at 60 ° C for 15 hours, and polymerized the A block. The polymerization rate was 99%.

To the reaction solution, a mixed solution of 54.3 g of DMAEMA, 0.41 g of AIBN, and 36.2 g of PMA, which had been previously substituted with argon, was added, and the reaction was carried out at 60 ° C for 10 hours to polymerize the B block. The polymerization rate was 98%.

After the reaction was completed, argon-substituted methanol (165 g) was added to the reaction solution and diluted, and 15.3 g of BzCl was added to the diluted solution, and the reaction was carried out at 60 ° C. for 10 hours to perform quaternization.

After the reaction was completed, the reaction solution was poured into stirred n-heptane. The precipitated polymer was suction-filtered and dried to obtain a block copolymer. The Mw of the obtained block copolymer was 7618, the PDI was 1.30, the acid value was 32 mgKOH / g, the amine value was 64 mgKOH / g, the A block content rate in the copolymer was 63% by mass, and the B block content rate was 37% by mass The content ratio of the structural unit derived from the vinyl monomer having an acidic group in the copolymer is 4.3% by mass, and the total of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the copolymer The content rate is 36.0% by mass. In addition, the content ratio of each structural unit in the copolymer was calculated from the vinyl monomer addition ratio used in the polymerization reaction, the vinyl monomer polymerization ratio, and the quaternization agent reaction ratio used in the quaternization reaction.

> Modulating Dispersant Composition>
(Dispersant composition No.A)
In a flask equipped with a stirrer, 87.5 g of block copolymer, 8.91 g of PI, 9.23 g of DBU, 110 g of PMA, and 110 g of MP were added, and the mixture was heated and mixed at 60 ° C for 20 hours to prepare a dispersant composition.

(Dispersant composition No.B ~ H)
The blending of each component was changed as shown in Table 1, and the dispersant composition Nos. B to H were obtained in the same manner as in the preparation method of the dispersant composition No. A.

【Table 1】

> Modified coloring composition>
(Coloring composition No. 1)
18 parts by mass of a pigment (CI Pigment Green 58, trade name: FASTOGEN (registered trademark) GREEN A310, manufactured by DIC Corporation), 12 parts by mass of a dispersant composition, and an alkali-soluble resin of a binder resin were put into a 500 ml mixing tank. Trade name: Ripoxy (registered trademark) SPC-2000, manufactured by Showa Polymer Co., Ltd.) 5.4 parts by mass and 64.6 parts by mass of PMA, and pre-dispersed by stirring at 2000 rpm using a disperser. To the obtained preliminary dispersion, 640 parts by mass of zirconia beads having a diameter of 0.5 mm was added, and the mixture was stirred at 2000 rpm for 2 hours to perform formal dispersion. 28.5 parts by mass of PMA was added to the obtained dispersion, and the mixture was further stirred at 1500 rpm for 10 minutes. The obtained final dispersion was filtered through a 2.5 μm mesh filter (trade name: HDC II Membrene Fillter, manufactured by PALL) to remove zirconia beads. The viscosity and brightness of the obtained colored composition were evaluated. The results are shown in Table 2.

(Coloring composition No. 2 to 8)
The dispersant was changed to Table 2 except that the coloring composition Nos. 2 to 8 were prepared in the same manner as the coloring composition No. 1 preparation method. In the coloring composition No. 8, the aforementioned block copolymer was used as a dispersant.

(Coloring composition No. 9)
Put a pigment (CI Pigment Blue 15: 6, trade name: FASTGEN (registered trademark) Blue A540, manufactured by DIC) into a mixing tank with an inner volume of 500 ml, 16 parts by mass, 24 parts by mass of a dispersant composition, and alkali solubility of a binder resin. 16 parts by mass of resin (trade name: Ripoxy (registered trademark) SPC-2000, manufactured by Showa Polymer Co., Ltd.) and 44 parts by mass of PMA were pre-dispersed by stirring at 2000 rpm for 10 minutes using a disperser. 640 parts by mass of zirconia beads having a diameter of 0.5 mm was added to the obtained preliminary dispersion, and the mixture was stirred at 2000 rpm for 2 hours to perform actual dispersion. 33.3 parts by mass of PMA was added to the obtained dispersion, and the mixture was further stirred at 1500 rpm for 10 minutes. The obtained final dispersion was filtered through a 2.5 μm mesh filter (trade name: HDC II Membrene Fillter, manufactured by PALL) to remove zirconia beads. The viscosity and brightness of the obtained colored composition were evaluated. The results are shown in Table 2.

(Coloring composition 10 ~ 11)
The coloring composition Nos. 10 and 11 were prepared in the same manner as the coloring composition No. 9 except that the dispersant was changed as shown in Table 2. In the coloring composition No. 11, the aforementioned block copolymer was used as a dispersant.
【Table 2】

The dispersant uses dispersant composition Nos. A to H and colored compositions Nos. 1 to 7, 9, and 10, which have high pigment dispersibility and low viscosity. Among these, the dispersant composition Nos. A to E and H contain a cyclic fluorene compound as a tertiary amine compound, and the dispersant composition Nos. A to E and H are used as the colored composition Nos. 1 to 5, 9 , 10 also has excellent coating film brightness. That is, the coloring compositions Nos. 1 to 5, 9, and 10 are excellent in discoloration resistance even when exposed to high temperatures in the process of manufacturing a liquid crystal display. When a color filter is produced using these coloring compositions, the brightness can be expected to increase.

The present invention includes the following embodiments.
(Implementation aspect 1)
A dispersant composition, which is a mixture of (a), (b), and (c), (a) a block copolymer, which has an A block and a B block, and the A block contains an acid source Is a structural unit of a vinyl monomer based on a base, the B block contains a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); (b) an aromatic dicarboxylic acid fluorene At least one aromatic compound selected from the group consisting of an amine, an aromatic compound containing an acidic group, and an aromatic compound containing a phenolic hydroxyl group; (c) a tertiary amine compound.

[Chemical Formula 19]
[In formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion. A

[Chemical Formula 20]
[In formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a ring structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. A

(Implementation aspect 2)
The dispersant composition according to embodiment 1, wherein the molar ratio of the quaternary ammonium salt group in the (a) block copolymer to the (b) aromatic compound ((b) / (a) Quaternary ammonium salt) is 0.5 ~ 1.2.

(Implementation aspect 3)
The dispersant composition according to embodiment 1 or 2, wherein the molar ratio ((c) / ( The quaternary ammonium salt in a)) is 0.5 to 1.2.

(Implementation aspect 4)
The dispersant composition according to any one of Embodiments 1 to 3, wherein the content ratio of the structural unit derived from the vinyl monomer having an acidic group in the (a) block copolymer is 1 mass % ~ 20% by mass.

(Implementation 5)
The dispersant composition according to any one of embodiments 1 to 4, wherein in the (a) block copolymer, the structural unit represented by the general formula (1) and the structure represented by the general formula (2) The total content of the units is 5 to 50% by mass.

(Implementation aspect 6)
The dispersant composition according to any one of embodiments 1 to 5, wherein the tertiary amine compound (c) is a compound represented by general formula (6) and / or a compound represented by general formula (7).

[Chemical Formula 21]
[In the general formula (6), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. R ⁶² and R ⁶³ may be bonded to each other to form a ring structure. A

[Chemical Formula 22]
[In the general formula (7), R ⁷¹ represents a divalent hydrocarbon group having 2 to 6 carbons which may have a substituent, and R ⁷² and R ⁷³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbons which may have a substituent. R ⁷² and R ⁷³ may be bonded to each other to form a ring structure. A

(Implementation aspect 7)
A coloring composition containing the dispersant composition described in any one of Embodiments 1 to 6, a coloring material, a dispersing medium, and a binder resin.

(Implementation aspect 8)
A coloring composition, which is a mixture of (a), (b), (c), a coloring material, a dispersing medium, and a binder resin, and (a) a block copolymer having A blocks and B blocks. The A block contains a structural unit derived from a vinyl monomer having an acidic group, and the B block contains a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); (b ) At least one aromatic compound selected from the group consisting of an aromatic dicarboxylic acid sulfonium imine, an acidic group-containing aromatic compound, and a phenolic hydroxyl group-containing aromatic compound; (c) a tertiary amine compound.

[Chemical Formula 23]
[In formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion. A

[Chemical Formula 24]
[In formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a ring structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. A

(Implementation aspect 9)
The coloring composition according to embodiment 7 or 8, wherein the coloring material is a phthalocyanin-based pigment.

(Implementation aspect 10)
The coloring composition according to any one of Embodiments 7 to 9, which is a color filter.

(Implementation aspect 11)
A color filter includes a colored layer formed using the colored composition described in the tenth aspect.
(Industrial availability)

The block copolymer of the present invention can be used as a dispersant for a coloring material of a coloring composition. The coloring composition is suitable for use in a color filter. The aforementioned color filters have high dimensional accuracy and are suitable for use in color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Claims (11)

A dispersant composition is obtained by mixing (a), (b), and (c), (a) a block copolymer having an A block and a B block, and the A block contains a A structural unit of an acidic vinyl monomer, the B block contains a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); (b) an aromatic dicarboxylic acid fluorene At least one aromatic compound selected from the group consisting of an imine, an aromatic compound containing an acidic group, and an aromatic compound containing a phenolic hydroxyl group; (c) a tertiary amine compound; [Chemical Formula 1] [In formula (1), R ¹¹ , R ^12, and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent, and two or more of R ¹¹ , R ^12, and R ¹³ may be bonded to each other to form a ring. Structure, X ¹ represents a divalent linking group, R ¹⁴ represents a hydrogen atom or a methyl group, and Y ^- represents a counter ion] [Chemical Formula 2] [In formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent, R ²¹ and R ²² may be bonded to each other to form a cyclic structure, and X ² represents a divalent linking group, R ²³ represents a hydrogen atom or a methyl group]. The dispersant composition according to claim 1, wherein the molar ratio of the quaternary ammonium salt group in the (a) block copolymer to the (b) aromatic compound ((b) / (a) The quaternary ammonium salt) is 0.5 to 1.2. The dispersant composition according to claim 1 or 2, wherein the molar ratio of the quaternary ammonium salt group in the (a) block copolymer to the (c) tertiary amine compound ((c) / (a The quaternary ammonium salt group in) is 0.5 to 1.2. The dispersant composition according to any one of claims 1 to 3, wherein the content ratio of the structural unit derived from the vinyl monomer having an acidic group in the (a) block copolymer is 1% by mass ~ 20% by mass. The dispersant composition according to any one of claims 1 to 4, wherein in the (a) block copolymer, the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) The total content rate is 5% to 50% by mass. The dispersant composition according to any one of claims 1 to 5, wherein the (c) tertiary amine compound is a compound represented by the general formula (6) and / or a compound represented by the general formula (7), [Chemical formula 3] [In the general formula (6), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ⁶² and R ⁶³ may be bonded to each other to form a cyclic structure] [Chemical Formula 4] [In the general formula (7), R ⁷¹ represents a divalent hydrocarbon group having 2 to 6 carbons which may have a substituent, and R ⁷² and R ⁷³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbons which may have a substituent, R ⁷² and R ⁷³ may be bonded to each other to form a ring structure]. A coloring composition containing the dispersant composition as described in any one of claims 1 to 6, a coloring material, a dispersing medium, and a binder resin. A coloring composition made by mixing (a), (b), (c), a coloring material, a dispersing medium, and a binder resin, (a) a block copolymer having A blocks and B blocks. The A block contains a structural unit derived from a vinyl monomer having an acidic group, and the B block contains a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); (b ) At least one aromatic compound selected from the group consisting of an aromatic dicarboxylic acid sulfonium imine, an acidic group-containing aromatic compound, and a phenolic hydroxyl group-containing aromatic compound; (c) a tertiary amine compound; [Chemical Formula 5 】 [In formula (1), R ¹¹ , R ^12, and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent, and two or more of R ¹¹ , R ^12, and R ¹³ may be bonded to each other to form a ring. Structure, X ¹ represents a divalent linking group, R ¹⁴ represents a hydrogen atom or a methyl group, and Y ^- represents a counter ion] [Chemical Formula 6] [In formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent, R ²¹ and R ²² may be bonded to each other to form a cyclic structure, and X ² represents a divalent linking group, R ²³ represents a hydrogen atom or a methyl group]. The coloring composition according to claim 7 or 8, wherein the coloring material is a phthalocyanin-based pigment. The coloring composition according to any one of claims 7 to 9, which is for a color filter. A color filter is provided with a coloring layer, and the coloring layer is formed using the coloring composition according to claim 10.