TWI788555B - Dispersant composition, coloring composition and color filter - Google Patents

Abstract

The object of the present invention is to provide a dispersant composition excellent in pigment dispersibility. The solution of the present invention is a dispersant composition, which is formed by mixing (a), (b) and (c), (a) block copolymer, which has an A block with an acidic group, and contains the general formula (1), B block of the structural unit shown in (2); (b) aromatic compound; (c) tertiary amine compound. [In the formulas (1) and (2), R11, R12, R13, R21 and R22 each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R11, R12, and R13 may be bonded to each other to form a ring structure. R21 and R22 may be bonded to each other to form a ring structure. R14 and R23 represent a hydrogen atom or a methyl group. X1 and X2 represent divalent linking groups. Y- means counter ion. ]

Description

Dispersant composition, coloring composition and color filter

The present invention relates to a dispersant composition, a colored composition containing the aforementioned dispersant composition, and a color filter having a colored layer formed using the aforementioned colored composition.

Conventionally, in the production of color filters used in liquid crystal displays and the like, pigment dispersion methods, dyeing methods, electroprinting methods, printing methods, and the like are known as methods for imparting coloring materials to substrates. These pigment dispersion methods are widely used from the viewpoints of spectroscopic properties, durability, pattern shape, and precision. In the pigment dispersion method, for example, a coating film composed of a coloring composition such as a mixed pigment, dispersant, and dispersing vehicle (solvent) is formed on a substrate, exposed through a photomask of a desired pattern shape, and alkaline development is performed.

In recent years, color filters are required to have higher transmission, high luminance, high contrast, and high color gamut. Therefore, various examinations have been carried out, such as increasing the concentration of pigments in coloring compositions, or developing pigments whose inherent transmission absorption spectrum is consistent with that of backlight phosphors, etc.

In particular, regarding the enhancement of the luminance of green pixels, novel zinc halide phthalocyanine green pigments having a specific hue have been proposed, as described in Patent Documents 1 and 2, for example. This enables higher luminance than conventional copper halide phthalocyanine green pigments. Also, Patent Document 3 has disclosed the use of a dispersant containing a structural unit derived from a vinyl monomer having a tertiary amino group and a structure derived from a vinyl monomer having a quaternary ammonium group. unit, the proportion of quaternary ammonium bases is less than 60 mole % of the total proportion of tertiary amine groups and quaternary ammonium bases. [Prior Technical Literature] [Patent Document]

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

[Problem 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 increases, making it difficult to industrially use the pigment dispersion to produce a colored resin composition. In addition, the dispersant used in the method of Patent Document 3 has insufficient pigment dispersibility. The present invention has been studied in view of the above circumstances, and an object of the present invention is to provide a dispersant composition excellent in pigment dispersibility. [Technical means to solve the problem]

The dispersant composition of the present invention that can solve the above-mentioned problems is formed by mixing (a), (b) and (c). (a) block copolymer has an A block and a B block, and the A block Containing a structural unit derived from a vinyl monomer with an acidic group, 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) is composed of aromatic At least one aromatic compound selected from the group consisting of aromatic dicarboxylic acid imide, acidic group-containing aromatic compound, and phenolic hydroxyl-containing aromatic compound; (c) tertiary amine compound.

〔式(1)中，R¹¹ 、R¹² 及R¹³ 分別獨立表示可具有取代基之鏈狀或環狀之烴基。R¹¹ 、R¹² 及R¹³ 中兩個以上可互相鍵結形成環狀構造。X¹ 表示二價連結基。R¹⁴ 表示氫原子或甲基。Y^- 表示對離子。〕[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 ^- indicates a counter ion. 〕

〔式(2)中，R²¹ 及R²² 分別獨立表示可具有取代基之鏈狀或環狀之烴基。R²¹ 及R²² 可互相鍵結形成環狀構造。X² 表示二價連結基。R²³ 表示氫原子或甲基。〕 ［對照先前技術之功效］[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. ] [Comparison with the efficacy of prior art]

Using the dispersant composition of the present invention can obtain a coloring composition with high dispersibility of coloring material and low viscosity. In particular, as (c) tertiary amine compound, if a cyclic amidine compound is used, the luminance of the coating film formed by the coloring composition can also be improved.

The dispersant composition of the present invention is formed by mixing (a), (b) and (c), (a) block copolymer has A block and B block, and the A block contains The structural unit of the vinyl monomer of the acidic group, the B block contains the structural unit shown in the following general formula (1) and the structural unit shown in the following general formula (2); (b) is composed of aromatic dicarboxylic acid imide 1. At least one aromatic compound selected from the group consisting of aromatic compounds containing acidic groups and aromatic compounds containing phenolic hydroxyl groups; (c) tertiary amine compounds.

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

In the present invention, "A block" can also be called "A block", and "B block" can also be called "B block". In the present invention, "vinyl monomer" refers to a monomer having a free radical polymerizable carbon-carbon double bond in the molecule. The "structural unit derived from a vinyl monomer" refers to a carbon-carbon double bond that can be polymerized by radical polymerization of a vinyl monomer to form a carbon-carbon single bond. "(Meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid". "(Meth)acrylate" is "at least one of acrylate and methacrylate". "(Meth)acryl" means "at least one of acryl and methacryl".

(A block) The A block is a polymer block, which has a structural unit derived from a vinyl monomer with an acidic group. The A block has an acidic group, thereby facilitating alkaline development. Therefore, the said block copolymer is suitable for the coloring composition for color filters used for manufacturing a color filter by alkaline image development.

The aforementioned acidic groups include carboxyl (-COOH), sulfonic acid (-SO ₃ H), phosphoric acid (-OPO ₃ H ₂ ), phosphonic acid (-PO ₃ H ₂ ), phosphonous acid (-PO ₂ H ₂ ). The A block may have only one kind of 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 aforementioned vinyl monomers with acidic groups are preferably at least one selected from vinyl monomers with carboxyl groups, vinyl monomers with sulfonic acid groups, or vinyl monomers with phosphoric acid groups. Among these, at least one selected from (meth)acrylic monomers having carboxyl groups, (meth)acrylic monomers having sulfonic acid groups, or (meth)acrylic monomers having phosphoric acid groups is preferred.

Vinyl monomers with carboxyl groups include (meth)acrylic acid; in 2-(meth)acryloxyethyl succinate, 2-(meth)acryloxyethyl maleate, Anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride, etc. The monomer of the reaction; crotonic acid; maleic acid; itaconic acid, etc.

Vinyl monomers with sulfonic acid groups include vinyl sulfonic acid, styrene sulfonic acid, disulfonic acid (meth) ethyl acrylate, methyl propyl sulfonic acid (meth) acrylamide, sulfonic acid ethyl Ester (meth)acrylamide, etc.

Examples of the vinyl monomer having a phosphoric acid group include 2-(phosphonyloxy)ethyl (meth)acrylate and the like.

The content of the structural unit derived from the vinyl monomer having an acidic group is preferably at least 2% by mass, more preferably at least 5% by mass, and more preferably at least 7% by mass in 100% by mass of the A block. Preferably it is 20 mass % or less, More preferably, it is 18 mass % or less, More preferably, it is 16 mass % or less. If the content of the structural unit derived from the vinyl monomer with an acidic group is 2% by mass or more, the dissolution rate will be fast when neutralized with alkali during alkaline development, and if it is 20% by mass or less, the hydrophilicity will not be Too high to suppress the resulting pixel noise.

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

Specific examples of vinyl monomers that can form other structural units of the A block include α-olefins, aromatic vinyl monomers, heterocyclic-containing vinyl monomers, vinyl amides, vinyl carboxylates, di Alkenes, (meth)acrylic monomers, etc. These vinyl monomers may have hydroxyl groups and epoxy groups.

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

(Meth)acrylic acid monomers include (meth)acrylic acid esters with chained alkyl groups (straight chain alkyl groups or branched chain alkyl groups); (meth)acrylic acid esters with cyclic alkyl groups (monocyclic structure) Esters; (meth)acrylates with aromatic ring groups; (meth)acrylamides; (meth)acrylates with polyalkylene glycol structural units; (meth)acrylates with hydroxyl groups; lactone modified Quality (meth)acrylates with hydroxyl groups; (meth)acrylates with alkoxy groups; (meth)acrylates with cyclic ether groups, etc.

Examples of (meth)acrylates with chain alkyl groups 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, etc. Examples of (meth)acrylates having a cyclic alkyl group include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, and cyclododecyl (meth)acrylate. Examples of (meth)acrylates having an aromatic ring group include benzyl (meth)acrylate, phenyl (meth)acrylate, and phenoxyethyl (meth)acrylate.

Examples of (meth)acrylamide include (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethyl (Meth)acrylamide, etc. (Meth)acrylates with polyalkylene glycol structural units include polyethylene glycol (polymerization degree=2~10) methyl ether (meth)acrylate, polyethylene glycol (polymerization degree=2~10 ) ethyl ether (meth) acrylate, polyethylene glycol (polymerization degree = 2~10) propyl ether (meth) acrylate, polyethylene glycol (polymerization degree = 2 ~ 10) phenyl ether (meth) (meth)acrylate with polyethylene glycol structural unit such as acrylate; polypropylene glycol (polymerization degree=2~10) methyl ether (meth)acrylate, polypropylene glycol (polymerization degree=2~10) Ethyl ether (meth)acrylate, polypropylene glycol (polymerization degree=2~10) propyl ether (meth)acrylate, polypropylene glycol (polymerization degree=2~10) phenyl ether (meth)acrylate, etc. (Meth)acrylates with polypropylene glycol structural units, etc.

Examples of (meth)acrylates with hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid hydroxyalkyl (meth)acrylate, etc., such as 4-hydroxybutyl ester.

The lactone-modified (meth)acrylate having a hydroxyl group includes adding lactone to the aforementioned (meth)acrylate having a hydroxyl group, preferably adding caprolactone. The added amount of lactone is preferably 1 mol to 10 mol, more preferably 1 mol to 5 mol. The aforementioned lactone-modified (meth)acrylates with hydroxyl groups include 1 mol adduct of 2-hydroxyethyl (meth)acrylate caprolactone, caprolactone of 2-hydroxyethyl (meth)acrylate 2mol adduct, 3mol adduct of caprolactone of 2-hydroxyethyl (meth)acrylate, 4mol adduct of caprolactone of 2-hydroxyethyl (meth)acrylate, 2-(meth)acrylic acid 5 mol adduct of caprolactone of hydroxyethyl ester, 10 mol adduct of caprolactone of 2-hydroxyethyl (meth)acrylate, etc.

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

Examples of (meth)acrylates with cyclic ether groups include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acrylmorpholine, (meth)acrylic acid 2-(4-Morpholinyl) ethyl ester, (3-ethyloxetan-3-yl) methyl (meth)acrylate, (2-methyl-2-ethyl) (meth)acrylate -1,3-dioxolane-4-yl)methyl ester, cyclic trimethylolpropane formal (meth)acrylate, (meth)acrylate 2-[(2-tetrahydropyranyl ) Oxy]ethyl ester, 1,3-dioxane-(meth)acrylate, etc.

The vinyl monomer that can form other structural units that can be contained in the A block is preferably a (meth)acrylic monomer, more preferably a (meth)acrylic ester with a chain alkyl group, a (meth)acrylic acid ester with an aromatic ring group ( Meth)acrylates, (meth)acrylates with polyalkylene glycol structural units, (meth)acrylates with hydroxyl groups, lactone-modified (meth)acrylates with hydroxyl groups, and cyclic ether groups At least one selected from the group consisting of (meth)acrylates. The aforementioned vinyl monomers that can be used in the A block can be used individually or in combination of two or more.

The A block has a group consisting of (meth)acrylates with chain alkyl groups, (meth)acrylates with cyclic alkyl groups, and (meth)acrylates with aromatic ring groups. When selecting at least one structural unit of a vinyl monomer, the total content of these structural units is preferably 30% by mass or more in 100% by mass of the A block, more preferably 35% by mass or more, and more preferably 40% by mass. More than 50% by mass, more preferably more than 60% by mass, more preferably more than 70% by mass, preferably less than 98% by mass, more preferably less than 95% by mass, and more preferably less than 95% by mass. Preferably, it is 90% by mass or less.

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

Also, the A block preferably does not have an amino group. That is, among the vinyl monomers constituting the A block, it is preferable not to contain a vinyl monomer having an amino group. If there are a lot of amine groups in the A block, when using a dispersant as a coloring material, the coloring material will be adsorbed to both the A block and the B block, and the dispersibility of the coloring material will be reduced. In the A block, the content of the structural unit derived from the vinyl monomer having an amino group is preferably at most 2% by mass, more preferably at most 1% by mass, still more preferably at most 0.1% by mass, most preferably at most 0.1% by mass. 0% by mass.

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

(B block) The B block is a polymer block, which 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 group in addition to the tertiary amine group, so it has high affinity with the coloring material.

(the structural unit shown in 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.

〔式(1)中，R¹¹ 、R¹² 及R¹³ 分別獨立表示可具有取代基之鏈狀或環狀之烴基。R¹¹ 、R¹² 及R¹³ 中兩個以上可互相鍵結形成環狀構造。X¹ 表示二價連結基。R¹⁴ 表示氫原子或甲基。Y^- 表示對離子。〕[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 ^- indicates a counter ion. 〕

The aforementioned chain hydrocarbon groups represented by R ¹¹ to R ¹³ include straight chain and branched chain. The substituents of the chain hydrocarbon groups represented by R ¹¹ to R ¹³ include halo, alkoxy, benzoyl (-COC ₆ H ₅ ), hydroxyl and the like. The substituents of the aforementioned cyclic hydrocarbon groups represented by R ¹¹ to R ¹³ include chain alkyl groups, halogen atoms, alkoxy groups, and hydroxyl groups.

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

The cyclic structure formed by two or more of R ¹¹ to R ¹³ being bonded to each other may be, for example, a nitrogen-containing monoheterocyclic ring with 5 to 7 membered rings or a condensed ring formed by condensing two of them. The nitrogen-containing heterocyclic ring is preferably non-aromatic, more preferably a saturated ring. Specifically, structures represented by the following formulas (1-1), (1-2), and (1-3) are mentioned.

〔通式(1-1)、(1-2)、(1-3)中，R¹⁵ 為R¹¹ ~R¹³ 之任一者。R¹⁶ 表示碳數1~6之烷基。l表示0~5之整數。m表示0~4之整數。n表示0~4之整數。*表示鍵結。l為2~5、m為2~4、n為2~4時，複數存在之R¹⁶ 分別可相同或相異。〕[chemical formula 4]

[In general formulas (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 a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, the plural R ¹⁶ may be the same or different, respectively. 〕

In the general formula (1), the divalent linking group X ¹ can be, for example, an alkylene group, an arylylene group, a -CONH-R ¹⁷ -group (amide group), and a -COO-R ¹⁸ -group with 1 to 10 carbon atoms. (ester group), etc., are preferably -CONH-R ¹⁷ -group and/or -COO-R ¹⁸ -group, more preferably -COO-R ¹⁸ -group. Also, the bonding direction of the amido group and the ester group is not particularly limited, but the bonding state of the amido group is preferably C-CO-NH-R ¹⁷ -N ⁺ R ¹¹ R ¹² R ¹³ , and the ester group is bonded A preferred aspect is C-CO-OR ¹⁸ -N ⁺ R ¹¹ R ¹² R ¹³ .

The aforementioned R ^is a single bond, an alkylene group with 1 to 10 carbons, or an ether group (alkyloxyalkyl group) with 1 to 10 carbons, preferably an alkylene group with 1 to 10 carbons, more preferably An alkylene group with 1 to 4 carbon atoms. Specific examples include methylene, ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and the like.

The aforementioned R ^is a single bond, an alkylene group with 1 to 10 carbons, or an ether group (alkyloxyalkyl group) with 1 to 10 carbons, preferably an alkylene group with 1 to 10 carbons, more preferably An alkylene group with 1 to 4 carbon atoms. Specific examples include methylene, ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and the like.

Y ^- includes halogen anions, carboxylate anions, nitroxide anions, sulfate anions, sulfonate anions, phosphate anions and the like.

Examples of the aforementioned halogen anion include fluoride anion, chloride anion, bromide anion, and iodide anion. Examples of the carboxylate anion include alkyl carboxylate anions such as acetate 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 methanesulfonate anion and ethanesulfonate anion; and aromatic sulfonate anions such as benzenesulfonate anion and toluenesulfonate anion. Examples of the phosphate anion include alkyl phosphate anions such as methyl phosphate anion and aromatic phosphate anions such as phenyl phosphate anion.

Specific examples of the vinyl monomer forming the structural unit represented by the aforementioned formula (1) include (meth)acryloxyethyltrimethylammonium chloride, (meth)acryloxypropyltrimethylammonium ammonium chloride, (meth)acryloxybutyltrimethylammonium chloride, (meth)acryloxyethylbenzyldimethylammonium chloride, (meth)acryloxypropyl benzyl dimethyl ammonium chloride, (meth)acryloxybutyl benzyl dimethyl ammonium chloride, (meth)acryloxy ethyl benzyl diethyl ammonium chloride, (methyl) Base) acryloxypropylbenzyldiethylammonium chloride, (meth)acryloxybutylbenzyldiethylammonium chloride, (meth)acrylamidopropylbenzyldiethylammonium Methylammonium chloride, (meth)acryloxyethyltrimethylammonium bromide, (meth)acryloxypropyltrimethylammonium bromide, (meth)acryloxybutyltrimethylammonium bromide Trimethylammonium bromide, (meth)acryloxyethylbenzyldimethylammonium bromide, (meth)acryloxypropylbenzyldimethylammonium bromide, (meth)acryl Acyloxybutylbenzyldimethylammonium bromide, (meth)acryloxyethylbenzyldiethylammonium bromide, (meth)acryloxypropylbenzyldiethylammonium bromide Ammonium, (meth)acryloxybutylbenzyldiethylammonium bromide, (meth)acrylamidepropylbenzyldimethylammonium bromide, (meth)acryloxyethylammonium Trimethylammonium iodide, (meth)acryloxypropyltrimethylammonium iodide, (meth)acryloxybutyltrimethylammonium iodide, (meth)acryloxypropyltrimethylammonium iodide Ethylbenzyldimethylammonium iodide, (meth)acryloxypropylbenzyldimethylammonium iodide, (meth)acryloxybutylbenzyldimethylammonium iodide, ( Meth)acryloxyethylbenzyldiethylammonium iodide, (meth)acryloxypropylbenzyldiethylammonium iodide, (meth)acryloxybutylbenzyldiethylammonium iodide Ethylammonium iodide, (meth)acryloxyethyltrimethylammonium fluoride, (meth)acryloxypropyltrimethylammonium fluoride, (meth)acryloxybutyl Trimethylammonium fluoride, (meth)acryloxyethylbenzyldimethylammonium fluoride, (meth)acryloxypropylbenzyldimethylammonium fluoride, (meth)acryl Acyloxybutylbenzyldimethylammonium fluoride, (meth)acryloxyethylbenzyldiethylammonium fluoride, (meth)acryloxypropylbenzyldiethylammonium fluoride Ammonium, (meth)acryloxybutylbenzyldiethylammonium fluoride, (meth)acryloxyethyltrimethylammonium = methylsulfate, (meth)acryloxypropyl Trimethylammonium = methylsulfate, (meth)acryloxybutyltrimethylammonium = methylsulfate, (meth)acryloxyethyldimethylethylammonium = ethyl Sulfate, (meth)acryloxypropyldimethylethylammonium = ethylsulfate, (meth)acryloxybutyldimethylethylammonium = ethylsulfate, (methyl ) Acryloxyethyltrimethylammonium = toluene-4-sulfonate, (meth)acryloxypropyltrimethylammonium = toluene-4-sulfonate, (meth)acryloxy Butyltrimethylammonium = toluene-4-sulfonate, (meth)acrylamidopropyltrimethylammonium = methylsulfate, (meth)acrylamidopropylethyl Dimethylammonium = Ethyl Sulfate etc.

The content of the structural unit represented by the general formula (1) is preferably at least 30% by mass, more preferably at least 35% by mass, more preferably at least 40% by mass, more preferably at least 85% by mass in 100% by mass of the B block % or less, more preferably less than 80 mass %, more preferably less than 75 mass %, still more preferably less than 60 mass %, still more preferably less than 50 mass %. 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.

(the structural unit shown in 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 type or two or more types.

〔式(2)中，R²¹ 及R²² 分別獨立表示可具有取代基之鏈狀或環狀之烴基。R²¹ 及R²² 可互相鍵結形成環狀構造。X² 表示二價連結基。R²³ 表示氫原子或甲基。〕[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. 〕

The chain hydrocarbon group represented by the aforementioned R ²¹ or R ²² includes straight chain and branched chain. The substituents of the chain hydrocarbon group represented by R ²¹ or R ²² include halo, alkoxy, benzoyl, hydroxyl and the like. The substituents of the cyclic hydrocarbon group represented by R ²¹ or R ²² include chain alkyl, halo, alkoxy, hydroxyl and the like.

The group represented by the aforementioned ^R21 or ^R22 is preferably an alkyl group with a carbon number of 1 to 4 that may have a substituent, an aralkyl group with a carbon number of 7 to 16 that may have a substituent, more preferably methyl, ethyl, Propyl, benzyl.

The cyclic structure formed by the aforementioned R ²¹ or R ²² being bonded to each other can be, for example, a nitrogen-containing monoheterocyclic ring with 5 to 7 membered rings or a condensed ring formed by condensation of two of these rings. The nitrogen-containing heterocyclic ring is preferably non-aromatic, more preferably a saturated ring. Specifically, structures represented by the following formulas (2-1), (2-2), and (2-3) are mentioned.

〔通式(2-1)、(2-2)、(2-3)中，R²⁴ 表示碳數1~6之烷基。l表示0~5之整數。m表示0~4之整數。n表示0~4之整數。*表示鍵結。l為2~5、m為2~4、n為2~4時，複數存在之R²⁴ 分別可相同或相異。〕[chemical formula 6]

[In the general formula (2-1), (2-2), (2-3), R ²⁴ represents an alkyl group with 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 a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, the plural R ²⁴ may be the same or different, respectively. 〕

In the above general formula (2), the divalent linking group X ² can be, for example, an alkylene group with 1 to 10 carbon atoms, an arylylene group, -CONH-R ²⁵ -yl (amide group), -COO-R ²⁶ - group (ester group), etc., 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 -group. In addition, the bonding direction of the amido group and the ester group is not particularly limited, and the bonding state of the amido group is preferably C-CO-NH-R ²⁵ -NR ²¹ R ²² , and the bonding state of the ester group is preferably C-CO-OR ²⁶ -NR ²¹ R ²² .

The aforementioned R ^is a single bond, an alkylene group with 1 to 10 carbons, or an ether group (alkyloxyalkyl group) with 1 to 10 carbons, preferably an alkylene group with 1 to 10 carbons, more preferably An alkylene group with 1 to 4 carbon atoms. Specific examples include methylene, ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and the like.

The aforementioned R ^is a single bond, an alkylene group with 1 to 10 carbons, or an ether group (alkyloxyalkyl group) with 1 to 10 carbons, preferably an alkylene group with 1 to 10 carbons, more preferably An alkylene group with 1 to 4 carbon atoms. Specific examples include methylene, ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and the like.

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

The B block may contain only the structural units represented by the general formula (1) and 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 units represented by the general formula (1) and the general formula (2) in the B block is preferably 80% by mass or more, and more preferably It is preferably at least 90% by mass, more preferably at least 95% by mass. Also, the B block preferably does not substantially contain a structural unit derived from a vinyl monomer having an acidic group. That is, the content rate of the structural unit derived from the vinyl monomer which has an acidic group is preferably 5 mass % or less in 100 mass % of B block, More preferably, it is 3 mass % or less.

Specific examples of the vinyl monomer that can form the other structural unit of the B block include the same ones that were exemplified as specific examples 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, the various structural units contained in the B block can be contained in any form such as random copolymerization or block copolymerization in the B block. From the viewpoint of uniformity, it is preferably Contained in the form of random copolymerization. For example, the B block can be formed by a copolymer of the structural unit constituted by the b1 block and the structural unit constituted by the b2 block.

(Block Copolymer) The structure of the aforementioned block copolymer is preferably a linear block copolymer. In addition, the linear block copolymer may have any structure (arrangement), but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the A block is expressed as A, and the B block is expressed as B When, it is _{preferred to} have at _least A structured copolymer. Among these, diblock copolymers represented by AB are preferable from the standpoint of workability during processing and compositional properties. By forming the diblock copolymer shown in AB, the A block can have a structural unit derived from a vinyl monomer with an acidic group, and the B block can have a vinyl monomer derived from a tertiary amino group. The structural unit of the base monomer and the structural unit derived from the vinyl monomer with a quaternary ammonium base are localized, and can effectively act on coloring materials, solvents, and adhesive resins (alkali-soluble resins).

The content of the A block is preferably at least 35% by mass, more preferably at least 40% by mass, more preferably at least 45% by mass, and still more preferably at least 50% by mass, based on 100% by mass of the entire block copolymer. , preferably 85% by mass or less, more preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 65% by mass or less. The content of the B block is preferably at least 15% by mass, more preferably at least 20% by mass, more preferably at least 25% by mass, and still more preferably at least 30% by mass, based on 100% by mass of the entire block copolymer. , preferably not more than 65 mass%, more preferably not more than 60 mass%, more preferably not more than 55 mass%, still more preferably not more than 50 mass%, especially not more than 45 mass%. By adjusting the content of the A block and the B block within the above range, it is possible to balance heat resistance and dispersing performance when used as a dispersant.

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

In the aforementioned (a) block copolymer, the content of the structural unit derived from the vinyl monomer having an acidic group is preferably at least 1% by mass, more preferably at least 2% by mass, and still more preferably at least 4% by mass. Above, preferably at most 20% by mass, more preferably at most 15% by mass, and more preferably at most 10% by mass.

In the block copolymer (a) above, 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 at least 5% by mass, more preferably at least 10% by mass , more preferably at least 20% by mass, more preferably at most 50% by mass, more preferably at most 45% by mass, and more preferably at most 40% by mass.

The molecular weight of the aforementioned (a) block copolymer was measured by gel permeation chromatography (hereinafter referred to as "GPC"). The weight average molecular weight (Mw) of the aforementioned (a) block copolymer is preferably at least 5,000, more preferably at least 6,000, more preferably at least 7,000, preferably at most 15,000, more preferably at most 12,000, and more preferably at least 12,000. Below 10000. When the weight average molecular weight is within the above-mentioned range, the dispersion performance when used as a dispersant becomes more favorable.

The molecular weight distribution (PDI) of the aforementioned (a) block copolymer is preferably 2.0 or less, more preferably 1.6 or less, still more preferably 1.4 or less. In addition, in the present invention, the molecular weight distribution (PDI) is obtained by (weight average molecular weight (Mw) of the block copolymer)/(number average molecular weight (Mn) of the block copolymer). The smaller the PDI is, the narrower the molecular weight distribution width is, and 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, it contains those with a small molecular weight and those with a large molecular weight.

(Manufacturing method of block copolymer) The production method of the above-mentioned block copolymers can be mentioned: the method of producing the A block first by the polymerization reaction of vinyl monomer, and then polymerizing the monomer of the B block in the A block; first producing the B block, and then in the The method of polymerizing the monomer of the A block in the B block; the method of coupling the A block and the B block after separately manufacturing the A block and the B block; first manufacturing the A block, and then polymerizing the B block containing the possible Form the monomer composition of the vinyl monomer of the structural unit represented by the formula (2), and then make the tertiary amine structure of a part of the structural unit represented by the formula (2) in the obtained polymer carry out the method of quaternization; polymerization containing can form The monomer composition of the vinyl monomer of the structural unit shown in formula (2), the monomer of the A block is polymerized in the polymer, so that the tertiary amine structure of a part of the structural unit shown in the formula (2) in the obtained polymer is carried out The method of quaternization; respectively manufacture A block and a block with a structural unit shown in formula (2), after coupling these blocks, make the tertiary amine of a part of the structural unit shown in formula (2) in the resulting polymer The method of constructing four levels, etc.

The polymerization method is not particularly limited, but living radical polymerization is preferred. That is, the aforementioned block copolymer is preferably polymerized by living radical polymerization. In the conventional radical polymerization method, not only the initiation reaction and the growth reaction will cause the growth end to be inactivated, but also the stop reaction and the chain transfer reaction will also cause the growth end to be inactivated, and it is easy to form a mixture of polymers with various molecular weights and non-uniform compositions. tendency. In this regard, the living radical polymerization method not only maintains the simplicity and versatility of the previous free radical polymerization method, but it is not easy to cause stop reaction or chain transfer, and can grow without deactivation at the growth end, so it is easy to manufacture molecular weight distribution. A homogeneous polymer is preferred at this point.

In the living radical polymerization method, the method of stabilizing the long end of the polymerization is different. There are methods using transition metal catalysts (ATRP method); methods using sulfur-based reversible chain transfer agents (RAFT method); and using organotellurium compounds. The method (TERP method) and other methods. The ATRP method uses amine complexes, so sometimes it cannot be used without protecting the acidic groups of vinyl monomers with acidic groups. In the RAFT method, it is difficult to form a low molecular weight distribution when using a variety of monomers, and there are defects such as sulfur odor and coloring. Among these methods, it is preferable to use the TERP method from the viewpoint of usable monomer diversity, molecular weight control in the polymer field, uniform composition, or coloring.

The TERP method refers to a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organotellurium compound as a polymerization initiator, for example, International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004 /072126 and the methods described in International Publication No. 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d). (a) A vinyl monomer is polymerized using an organotellurium compound represented by the general formula (11). (b) Polymerizing a vinyl monomer using a mixture of an organotellurium compound represented by general formula (11) and an azo-based polymerization initiator. (c) Polymerizing a vinyl monomer using a mixture of an organotelluride 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 organotelluride compound represented by the general formula (11), an azo-based polymerization initiator, and an organic ditelluride compound represented by the general formula (12).

[通式(11)中，R¹ 表示碳數1~8之烷基、芳基或芳香族雜環基。R² 及R³ 分別獨立表示氫原子或碳數1~8之烷基。R⁴ 表示碳數1~8之烷基、芳基、取代芳基、芳香族雜環基、烷氧基、醯基、醯胺基、氧羰基、氰基、烯丙基或炔丙基。 通式(12)中，R¹ 表示碳數1~8之烷基、芳基或芳香族雜環基。][chemical formula 7]

[In the general formula (11), R ¹ represents an alkyl, aryl or aromatic heterocyclic group with 1 to 8 carbon atoms. R ² and R ³ independently represent a hydrogen atom or an alkyl group having 1 to 8 carbons. R ⁴ represents an alkyl group, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, acyl group, amido 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 ^R1 is an alkyl group with 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group, specifically as follows. Alkyl groups with 1 to 8 carbons include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, pentyl, hexyl, heptyl , straight chain or branched chain alkyl such as octyl, or cyclic alkyl such as cyclohexyl, etc. It is preferably a linear or branched chain alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group. Examples of the aryl group include phenyl, naphthyl and the like. Examples of the aromatic heterocyclic group include pyridyl, furyl, thienyl and the like.

The groups represented by ^R2 and ^R3 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is specifically as follows. Alkyl groups with 1 to 8 carbons include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, pentyl, hexyl, heptyl , straight chain or branched chain alkyl such as octyl, or cyclic alkyl such as cyclohexyl, etc. It is preferably a linear or branched chain alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

The group represented by ^R4 is an alkyl group, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, acyl group, amido group, oxycarbonyl group, cyano group, allyl group or alkyne group with 1 to 8 carbon atoms The propyl group is specifically as follows. Alkyl groups with 1 to 8 carbons include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, pentyl, hexyl, heptyl , octyl and other linear or branched chain alkyl groups, cyclohexyl and other cyclic alkyl groups, and the like. It is preferably a linear or branched chain alkyl group with 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. Examples of the aryl group include phenyl, naphthyl and the like. Preferably it is phenyl. As a substituted aryl group, the phenyl group which has a substituent, the naphthyl group which has a substituent, etc. are mentioned. The substituents of the aforementioned aryl groups with substituents can be, for example, halogen atoms, hydroxyl groups, alkoxy groups, amino groups, nitro groups, cyano groups, carbonyl-containing groups represented by -COR ⁴¹¹ (R ⁴¹¹ is a carbon number of 1 to 8 Alkyl, aryl, alkoxy or aryloxy with 1 to 8 carbons), sulfonyl, trifluoromethyl, etc. Also, one or two of these substituents may be substituted. Examples of the aromatic heterocyclic group include pyridyl, furyl, thienyl and the like. An alkoxy group is preferably an alkyl group with 1 to 8 carbon atoms bonded to an oxygen atom, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, and second butyl Oxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, etc. Examples of the acyl group include acetyl, propionyl, benzoyl and the like. Examples of the amido group include -CONR ⁴²¹ R ⁴²² (R ⁴²¹ and R ⁴²² are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms). Oxycarbonyl is preferably a group represented by -COOR ⁴³¹ (R ⁴³¹ is a hydrogen atom, an alkyl or aryl group with 1 to 8 carbons), such as carboxyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl , n-butoxycarbonyl, second butoxycarbonyl, third butoxycarbonyl, n-pentyloxycarbonyl, phenoxycarbonyl, etc. Preferable oxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl. Allyl can include -CR ⁴⁴¹ R ⁴⁴² -CR ⁴⁴³ =CR ⁴⁴⁴ R ⁴⁴⁵ (R ⁴⁴¹ and R ⁴⁴² are independently hydrogen atoms or alkyl groups with 1 to 8 carbons, and R ⁴⁴³ , R ⁴⁴⁴ and R ⁴⁴⁵ are independently It is a hydrogen atom, an alkyl group or an aryl group with 1 to 8 carbon atoms, each substituent can be connected in a ring structure), etc. Examples of propargyl include -CR ⁴⁵¹ R ⁴⁵² -C≡CR ⁴⁵³ (R ⁴⁵¹ and R ⁴⁵² are hydrogen atoms or alkyl groups with 1 to 8 carbons, R ⁴⁵³ are hydrogen atoms or alkyl groups with 1 to 8 carbons, aryl or silyl), etc.

Organotellurium compounds represented by general formula (11) specifically include (methyltellurylmethyl)benzene, (methyltellurylmethyl)naphthalene, ethyl-2-methyl-2-methyltelluryl -propionate, ethyl-2-methyl-2-n-butyltelluryl-propionate, (2-trimethylsilyloxyethyl)-2-methyl-2-methyltelluryl- Propionate, (2-Hydroxyethyl)-2-methyl-2-methyltelluryl-propionate, or (3-trimethylsilylpropargyl)-2-methyl-2-methanoate All organotellurium compounds described in International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and International Publication No. 2004/096870.

Specific examples of organic ditelluride compounds represented by the general formula (12) include, for example, dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, bicyclo Propyl ditelluride, di-n-butyl ditelluride, di-second butyl ditelluride, di-tertiary butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis-( p-methoxyphenyl) ditelluride, bis-(p-aminophenyl) ditelluride, bis-(p-nitrophenyl) ditelluride, bis-(p-cyanophenyl) ditelluride, Bis-(p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride, or dipyridyl ditelluride, etc.

As the azo-based polymerization initiator, an azo-based polymerization initiator used in general radical polymerization can be used without any particular limitation. Examples include 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-acetyloxy-1-phenylethane), 2, 2'-Azobis(2-methylbutylamide), 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70), 2, 2'-Azobis(2-methylformamidinopropane) dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'- Azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2,4,4-trimethylpentane), 2-cyano- 2-Propyl azoformamide, 2,2'-azobis(N-butyl-2-methylpropionamide), or 2,2'-azobis(N-cyclohexyl-2- methacrylamide), etc.

The polymerization step is to mix the vinyl monomer and the organotellurium compound of the general formula (11) in a container replaced by an inert gas, and further mix azo It is a polymerization initiator and/or an organic ditelluride compound of general formula (12). In this case, examples of the inert gas include nitrogen, argon, helium and the like. Argon and nitrogen are preferred.

In the aforementioned (a), (b), (c) and (d), it is only necessary to appropriately adjust the usage amount of the vinyl monomer according to the physical properties of the target copolymer. Preferably, the vinyl monomer is 5 mol to 10000 mol relative to 1 mol of the organotellurium 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 in (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 in combination in the aforementioned (c), the organic ditelluride compound of the general formula (11) is 1 mol, and the organic ditelluride compound of the general formula (12) is The telluride compound is preferably 0.01 mol to 100 mol.

When the organic telluride compound of the general formula (11) and the organic ditelluride compound of the general formula (12) and the azo-based polymerization initiator are used in combination in (d), relative to 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 carried out even without a solvent, and the above-mentioned mixture can be stirred using an aprotic solvent or a protic solvent generally used in radical polymerization to carry out the polymerization reaction. The aprotic solvents that can be used can for example be anisole, benzene, toluene, N,N-dimethylformamide (DMF), dimethylsulfoxide (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, etc. In addition, the protic solvent can be, for example, water, methanol, ethanol, isopropanol, n-butanol, ethylcellosulo, butylcellosulo, 1-methoxy-2-propanol, hexafluoroisopropanol or diacetone alcohol etc.

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

The reaction temperature and reaction time can be appropriately adjusted according to the molecular weight or molecular weight distribution of the obtained copolymer, usually stirring 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 normal pressure, but it may be increased or reduced.

After the completion of the polymerization reaction, the used solvent, residual vinyl monomer, etc. are removed from the obtained reaction mixture by general separation and purification means, and the target copolymer can be isolated.

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

The growth end of the copolymer obtained by the polymerization reaction is in the form of -TeR ¹ (where R ¹ is the same as above) derived from the tellurium compound. After the polymerization reaction, it will be inactivated when it is operated in the air, but the tellurium atom will remain . Copolymers in which tellurium atoms remain at the end may be colored or have poor thermal stability, so it is preferable to remove tellurium atoms.

Methods for removing tellurium atoms can be used: Free radical reduction methods using tributylstannane or thiol compounds; Adsorption methods such as activated carbon, silica gel, activated alumina, activated clay, molecular sieves, and polymer adsorbents; ion exchange resins; and other methods of adsorbing metals; Add peroxides such as hydrogen peroxide or benzoyl peroxide, or blow air or oxygen into the system to oxidatively decompose the tellurium atoms at the end of the copolymer, and wash with water or a suitable solvent to remove residual tellurium compounds Liquid-liquid extraction or solid-liquid extraction; Purification methods such as ultrafiltration in a solution state to remove only those with a specific molecular weight or less; Also, these methods can be used in combination.

When the tertiary amine group of the structural unit shown in formula (2) carries out quaternization, quaternization agent can enumerate halogenated alkyl such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide; Benzyl chloride, benzyl bromide, benzyl Aralkyl halides such as base iodide; diaryl sulfate such as diphenyl sulfate; dimethyl sulfate; dialkyl sulfate such as diethyl sulfate and di-n-propyl sulfate; methyl p-toluenesulfonate, p-toluenesulfonate Aromatic sulfonic acid alkyl esters such as ethyl acetate, etc. Of 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 sulfonate alkyl esters such as esters and ethyl p-toluenesulfonate, more preferably benzyl chloride, dimethyl sulfate, and methyl p-toluenesulfonate. The structure after quaternization introduces alkyl and aralkyl groups derived from quaternization agents. Therefore, by measuring the amount of the alkyl group and aralkyl group introduced by quaternization, the amount of the structural unit represented by the formula (1) can be estimated.

The method of quaternizing the tertiary amine structure of a part of the structural unit represented by the formula (2) in the polymer includes a method of bringing the polymer into contact with a quaternization agent. Specifically, a method of adding a quaternizing agent to the reaction solution after polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit represented by formula (2) and stirring it is exemplified. The temperature of the reaction liquid for adding the quaternizing agent is preferably 25°C~65°C, more preferably 55°C~65°C, and the stirring time is preferably 1 hour~40 hours, more preferably 5 hours~20 hours. When adding a quaternization agent, it is preferable to dilute the reaction liquid after polymerization. Solvents to be added for dilution include solvents usable in polymerization, protic solvents, and mixed solvents of solvents used in polymerization and protic solvents, and may be appropriately selected according to the solubility of the target block copolymer. The protic solvent is more preferably methanol.

(b) Aromatic compounds The dispersant composition of the present invention contains (b) at least one aromatic compound selected from the group consisting of aromatic dicarboxylic acid imides, acidic group-containing aromatic compounds, and phenolic hydroxyl-containing aromatic compounds. The dispersant composition improves dispersibility by containing (b) an aromatic compound. (b) Aromatic compounds may be blended alone or in combination of two or more.

The aromatic dicarboxylic acid imide has an aromatic ring and an imide group (-C(=O)NHC(=O)-) directly bonded to the aromatic ring in the molecule. Both ends of the above-mentioned imide group may be bonded to one aromatic ring, or may be bonded to different aromatic rings respectively, but preferably both ends are bonded to one aromatic ring. The aforementioned aromatic dicarboxylic acid imide is preferably a compound represented by general formula (3).

〔通式(3)中，環A表示可具有取代基之芳香環。〕[chemical formula 8]

[In general formula (3), ring A represents an aromatic ring which may have a substituent. 〕

In the general formula (3), the aromatic ring constituting the ring A has an aromatic ring structure. The aforementioned aromatic ring includes a single ring and a condensed ring. The aforementioned single ring is preferably a 5- or 6-membered ring, preferably a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring. The aforementioned condensed rings are preferably 2 to 5 condensed rings, preferably naphthalene rings, anthracene rings, phenanthrene rings, and indole rings. Among these, the atom constituting the ring structure in the ring structure does not contain heteroatoms. Examples of substituents that the aforementioned 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 aforementioned aromatic dicarboxylic acid imides include the following compounds.

[chemical formula 9]

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

〔通式(4)中，環A表示可具有取代基之芳香環。〕[chemical formula 10]

[In general formula (4), ring A represents an aromatic ring which may have a substituent. 〕

In the general formula (4), the aromatic ring constituting the ring A has an aromatic ring structure. The aforementioned aromatic ring includes a single ring and a condensed ring. The aforementioned single ring is preferably a 5- or 6-membered ring, preferably a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring. The aforementioned condensed rings are preferably 2 to 5 condensed rings, preferably naphthalene rings, anthracene rings, phenanthrene rings, and indole rings. Among these, the atom constituting the ring structure in the ring structure does not contain heteroatoms. Examples of substituents that the aforementioned 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.

The above-mentioned aromatic carboxylic acid specifically includes the following compounds.

[chemical formula 11]

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

[chemical formula 12]

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

[chemical formula 13]

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

〔通式(5)中，環A表示可具有取代基之芳香環。〕[chemical formula 14]

[In general formula (5), ring A represents an aromatic ring which may have a substituent. 〕

In the general formula (5), the aromatic ring constituting the ring A has an aromatic ring structure. The aforementioned aromatic ring includes a single ring and a condensed ring. The aforementioned single ring is preferably a 5- or 6-membered ring, preferably a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring. The aforementioned condensed rings are preferably 2 to 5 condensed rings, preferably naphthalene rings, anthracyclines, phenanthrene rings, indole rings, coumarin rings, and xanthene rings. Examples of substituents that the aforementioned 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 above-mentioned phenolic hydroxyl group-containing aromatic compound include the following compounds.

[chemical formula 15]

(c) Tertiary amine compound The aforementioned dispersant composition contains (c) a tertiary amine compound. The aforementioned (c) tertiary amine compound has a tertiary amine structure in the molecule. The dispersant composition contains (c) a tertiary amine compound, thereby forming a salt with the aforementioned (b) aromatic compound. (c) The tertiary amine compound may be compounded only by 1 type or in combination of 2 or more types.

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

〔通式(6)中，R⁶¹ 、R⁶² 及R⁶³ 分別獨立表示可具有取代基之碳數1~10之烴基。又，R⁶² 及R⁶³ 可互相鍵結形成環狀構造。〕[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. In addition, R ⁶² and R ⁶³ may be bonded to each other to form a ring structure. 〕

The hydrocarbon groups with 1 to 10 carbons represented by R ⁶¹ , R ⁶² and R ⁶³ include chain alkyls with 1 to 10 carbons, cyclic alkyls with 1 to 10 carbons, and aryl groups with 6 to 10 carbons , an aralkyl group with 7 to 10 carbons, and an alkylaryl group with 7 to 10 carbons.

Compounds represented by general formula (6) include trimethylamine, triethylamine, diisopropylethylamine, trin-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N-ethyl Aliphatic amines such as dipentylamine; aromatic amines such as N,N-dimethylaniline and N,N-diethylaniline; N,N-dimethyl-cyclohexylamine, N,N-diethyl- Alicyclic amines such as cyclohexylamine, etc.

〔通式(7)中，R⁷¹ 表示可具有取代基之碳數2~6之二價烴基，R⁷² 及R⁷³ 分別獨立表示氫原子或可具有取代基之碳數1~10之烴基。又，R⁷² 及R⁷³ 可互相鍵結形成環狀構造。〕[chemical formula 17]

[In the general formula (7), R ⁷¹ represents a divalent hydrocarbon group with 2 to 6 carbon atoms that may have a substituent, and R ⁷² and R ⁷³ independently represent a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms that may have a substituent. In addition, R ⁷² and R ⁷³ may be bonded to each other to form a ring structure. 〕

The divalent hydrocarbon group having 2 to 6 carbon atoms represented by R ⁷¹ includes an alkylene group having 2 to 6 carbon atoms. The substituents of the hydrocarbon group with divalent carbon number 2~6 represented by ^R71 mentioned above include chain alkyl group with 1~10 carbon number, cyclic alkyl group with 1~10 carbon number, and aromatic group with 6~10 carbon number. group, aralkyl group with 7 to 10 carbons, and alkylaryl group with 7 to 10 carbons.

The hydrocarbon groups with 1 to 10 carbons represented by R ⁷² and R ⁷³ include chain alkyls with 1 to 10 carbons, cyclic alkyls with 1 to 10 carbons, aryl groups with 6 to 10 carbons, Aralkyl groups with 7 to 10 carbon atoms, and alkylaryl groups with 7 to 10 carbon atoms.

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

〔通式(8)中，R^80~ R⁸⁹ 係分別獨立表示氫原子、碳數1~10之烷基、碳數6~10之芳基。n為1~4之整數。m為1~4之整數。〕[chemical formula 18]

[In the general formula (8), R80 ^{~ R89} independently represent a hydrogen atom, an alkyl group with 1~10 carbons, and an aryl group with 6~10 carbons. n is an integer from 1 to 4. m is an integer from 1 to 4. 〕

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

[chemical formula 19]

The aforementioned dispersant composition preferably contains a solvent. The aforementioned solvent can use an organic solvent, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tertiary butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monoethyl ether 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 base ethers; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di Propyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether and other glycol dialkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methyl acetate Oxybutyl acetate, 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-acetic acid Diol alkyl ether acetates such as methoxybutyl ester; diol diacetic acid such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanol diacetate Esters; alkyl acetates such as cyclohexanol acetate; amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, dipentyl ether, ethyl Diisobutyl ether, dihexyl ether and other ethers; acetone, methyl ethyl ketone, methyl pentanone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone , cyclohexanone, ethyl pentanone, methyl butanone, methyl hexanone, methyl nonanone, methoxymethyl pentanone and other ketones; ethanol, propanol, butanol, hexanol, cyclohexanol , ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, methoxymethylpentanol, glycerin, benzyl alcohol and other monohydric or polyhydric alcohols; Pentane, n-octane, isobutene, n-hexane, hexene, isoprene, dipentene, dodecane and other aliphatic hydrocarbons; cyclohexane, methylcyclohexane, methylcyclohexene, Alicyclic hydrocarbons such as dicyclohexyl; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate , methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate , ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxy propyl propionate, butyl 3-methoxypropionate, γ-butyrolactone and other chain or cyclic esters; 3-methoxypropionic acid, 3-ethoxypropionic acid and other alkoxy carbox Acids; halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile, etc. The organic solvent contained in the dispersant composition may be only one type or a plurality of types.

The aforementioned dispersant composition can be prepared by mixing (a) a block copolymer, (b) an aromatic compound, (c) a tertiary amine compound, and an optional solvent. Also, it is considered that (b) aromatic compound and (c) tertiary amine compound react to form an organic salt after mixing, so the mixture of (b) aromatic compound and (c) tertiary amine compound can be mixed in advance (such as (d) ) a salt composed of an aromatic compound and a tertiary amine compound) and (a) a block copolymer. The mixing of each raw material can be performed using mixing and dispersing machines such as a paint shaker, a bead mill, a ball mill, a dissolver, and a kneader, for example. When preparing the dispersant composition, the mixing temperature is preferably above 50°C, more preferably above 55°C, more preferably above 60°C, preferably below 75°C, more preferably below 70°C, and more preferably at 65°C below ℃.

In the aforementioned dispersant composition, the molar ratio of the aforementioned (a) quaternary ammonium base in the block copolymer to the aforementioned (b) aromatic compound (quaternary ammonium base in (b)/(a)) It is preferably at least 0.5, more preferably at least 0.8, more preferably at least 1.0, more preferably at most 1.2, more preferably at most 1.1, and more preferably at most 1.05.

In the aforementioned dispersant composition, the molar ratio of the quaternary ammonium base in the aforementioned (a) block copolymer to the aforementioned (c) tertiary amine compound ((c)/quaternary ammonium base in (a) ) is preferably at least 0.5, more preferably at least 0.8, more preferably at least 1.0, more preferably at most 1.2, more preferably at most 1.1, and more preferably at most 1.05.

In the aforementioned dispersant composition, the molar ratio ((c)/((a) The acidic group+(b)) in is preferably 0.1 or more, more preferably 0.3 or more, more preferably 0.5 or more, preferably 1.0 or less, more preferably 0.9 or less, and more preferably 0.8 or less.

In the aforementioned dispersant composition, the molar ratio ((b)/(c)) of the aforementioned (b) aromatic compound to the aforementioned (c) tertiary amine compound is preferably at least 0.9, more preferably at least 0.95, and even more preferably Preferably, it is 1.0 or more, More preferably, it is 1.1 or less, More preferably, it is 1.05 or less, More preferably, it is 1.02 or less.

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

The acid value of the solid content of the aforementioned dispersant composition is preferably at least 5 mgKOH/g, more preferably at least 10 mgKOH/g, more preferably at least 15 mgKOH/g, preferably at most 70 mgKOH/g, more preferably at least 65 mgKOH/g Below, more preferably below 60mgKOH/g. If the acid value is more than 5mgKOH/g, the solubility to alkali is high, and the speed of dissolving in alkali is faster. If the acid value is less than 70mgKOH/g, the viscosity of the coloring composition will not be too high, and the coatability of the photoresist composition will be better. . Here, solid content is a component other than a solvent.

The amine value of the solid content of the aforementioned dispersant composition is preferably at least 10 mgKOH/g, more preferably at least 30 mgKOH/g, still more preferably at least 50 mgKOH/g, preferably at most 150 mgKOH/g, more preferably at least 120 mgKOH/g Below, more preferably below 95mgKOH/g. If the amine value is 10 mgKOH/g or more, the stability of the viscosity of the coloring composition over time is further improved, and if it is 150 mgKOH/g or less, the viscosity increase of the coloring composition can be suppressed.

(coloring composition) The coloring composition of the present invention contains the aforementioned dispersant composition, a coloring material, a dispersing vehicle, and a binder resin.

(coloring material) The kind of said coloring material can be selected suitably according to the use, For example, a pigment and a dye are mentioned. It is preferable that the said coloring composition contains a pigment as a coloring material from a viewpoint of light resistance and heat resistance. The pigment may be either an organic pigment or an inorganic pigment, but is particularly preferably an organic pigment mainly composed of an organic compound. As a pigment, various color pigments, such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, and a purple pigment, are mentioned, for example. Examples of the pigment structure include azo-based pigments such as monoazo-based pigments, diazo-based pigments, and condensed diazo-based pigments, diketopyrrolopyrrole-based pigments, phthalocyanine-based pigments, isoindolinone-based pigments, and isoindolinone-based pigments. Polycyclic pigments such as indoline pigments, quinacridone pigments, indigo pigments, thioindigo pigments, quinoline yellow pigments, bisoxazine pigments, anthraquinone pigments, perylene pigments, and perinone 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 adjusting chromaticity and the like.

Specific examples of pigments include C.I. 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; C. I. 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; C. I. Pigment Orange 36, 38, 43 and other orange pigments; C. I. Pigment Blue 15, 15:1, 15:2, 15: 3, 15: 4, 15: 6, 16, 17, 22, 60 and other blue pigments; C. I. Pigment Green 7, 36, 58, 59, 62, 63, aluminum phthalocyanine, polyhalide aluminum phthalocyanine, aluminum Phthalocyanine hydroxide, diphenoxyphosphinoaluminum phthalocyanine, diphenylphosphinoaluminum phthalocyanine, polyhalogenated diphenoxyphosphinoaluminum phthalocyanine, polyhalogenated diphenylphosphine Green pigments such as aluminum oxide phthalocyanine; purple pigments such as C. I. Pigment Violet 23, 32, 50, etc. Among these, the pigments are preferably C. I. Pigment Red 254, C. I. Pigment Red 255, C. I. Pigment Red 264, C. I. Pigment Red 269, C. I. Pigment Blue 15, C. I. Pigment Blue 15:2, C. I. Pigment Blue 15:3, C. I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, etc.

In the present invention, the dispersant composition is preferably used together with a coloring material containing a phthalocyanine pigment, specifically, it is preferably used with a coloring material containing Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 17, Pigment Green 7, C. I. Pigment Green 36, C. I. Pigment Green 58, C. I. Pigment Green 59, C. I. Pigment Green 62, C. I. Pigment Green 63, Aluminum Phthalocyanine, polyhalide aluminum phthalocyanine, aluminum phthalocyanine hydroxide, diphenoxyphosphinoaluminum phthalocyanine, diphenylphosphinoaluminum phthalocyanine, polyhalogenated diphenoxyaluminum phthalocyanine It is used together with coloring materials such as oxyaluminum phthalocyanine and polyhalogenated diphenylphosphinooxyaluminum phthalocyanine. More preferably, it is used together with a coloring material containing a polyhalogenated phthalocyanine pigment.

When forming a light-shielding material such as a black matrix of a color filter using the coloring composition of the present invention, a black pigment can be used. The black pigment may be used alone, or may be used in combination with the aforementioned red pigment, the aforementioned green pigment, the aforementioned blue pigment, or the like. Examples of black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoint of light-shielding ratio and image characteristics.

The number average particle diameter of the said coloring material can be suitably selected according to the use, and is not specifically limited. From the viewpoint of high transparency and high contrast, the aforementioned coloring composition preferably contains coloring materials with a number average particle size of 10 nm to 150 nm.

The aforementioned coloring material may contain a pigment derivative as a dispersion aid. In order to bond and adsorb ions with tertiary amine groups and quaternary ammonium salt groups in the resin-type dispersant, the aforementioned pigment derivatives are preferably acidic pigment derivatives containing acidic groups. The pigment derivative is one in which an acidic functional group is introduced into the pigment skeleton. The pigment skeleton is preferably the same or similar skeleton as the coloring material constituting the coloring composition, or the same or similar skeleton as the compound of the coloring material raw material. Specific examples of the dye skeleton include an azo dye skeleton, a phthalocyanine dye skeleton, an anthraquinone dye skeleton, a triazine dye skeleton, an acridine dye skeleton, a perylene dye skeleton, and the like. The acidic group introduced into the pigment skeleton is preferably a carboxyl group, a phosphoric acid group, or a sulfonic acid group. Also, in terms of synthesis convenience and acidity strength, a sulfonic acid group is preferred. In addition, the acidic group can be directly bonded to the pigment skeleton, or can 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, for example, it is preferably 4 to 17 parts by mass relative to 100 parts by mass of the coloring material.

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

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

(dispersion medium) In the above-mentioned 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, a conventionally known organic solvent can be used, and those exemplified as the solvent of the above-mentioned dispersant composition can be used. The organic solvent is preferably glycol alkyl ether acetates, monohydric or polyhydric alcohols, from the viewpoint of dispersibility of coloring materials and the like, solubility of dispersants, coating properties of colored compositions, and the like. The solvent contained in the coloring composition may be only one kind or plural kinds.

When the color filter pixels are formed by photolithography, the boiling point of the dispersion medium is preferably 100°C~200°C (under the pressure of 1013.25hPa. The following are the same about the boiling point.), more preferably 120°C~170°C . Among the above-mentioned dispersion media, glycol alkyl ether acetates are preferable in view of good balance between coatability, surface tension, etc., and high solubility of constituent components in the coloring composition. Glycol alkyl ether acetates can be used alone or in combination with other dispersing media. In addition, at this time, it is preferable to use together a dispersion medium having a boiling point of 150° C. or higher. By using the dispersing medium with such a high boiling point in combination, it is possible to make the coloring composition difficult to dry, and it is possible to suppress the destruction of the mutual relationship of the coloring composition due to rapid drying. The content ratio of the dispersion medium having a boiling point of 150° C. or higher is preferably 3% by mass 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 generation of foreign matter defects due to precipitation and solidification of the coloring material and the like at the tip of the slit nozzle. If it is 50% by mass or less, the drying speed of the coloring composition will be slowed down, and the prolongation of the drying time and the occurrence of prebaking pin marks in the production of the color filter described later can be suppressed. In addition, the dispersing medium having a boiling point of 150° C. or higher may be glycol alkyl ether acetates, and in this case, it does not matter if the dispersing medium having a boiling point of 150° C. or higher is not included separately.

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, more preferably 150°C to 280°C. The uniformity of the obtained coating film can be made favorable by making a boiling point 130 degreeC or more. 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, and poor quality and prolonged drying time can be suppressed. In addition, from the viewpoint of the uniformity of the obtained coating film, the vapor pressure of the dispersion medium can be used usually below 10 mmHg, preferably below 5 mmHg, more preferably below 1 mmHg.

In addition, when color filters are produced by the inkjet method, the ink ejected from the nozzle is only a few pL to tens of pL, which is very fine, so the dispersion medium evaporates around the nozzle or before it is attached to the pixel library. Ink tends to concentrate and dry. In order to avoid this, it is preferable that the boiling point of the dispersing medium is high, and specifically, it is preferable to contain a dispersing medium having a boiling point of 180° C. or higher. More preferably, it contains a dispersion medium with a boiling point of 200°C or higher, and particularly preferably, it contains a dispersion medium with a boiling point of 220°C or higher. Also, the high boiling point solvent having a boiling point of 180°C or higher is preferably at least 50% by mass, more preferably at least 70% by mass, most preferably at least 90% by mass, based on 100% by mass of the entire dispersing medium contained in the coloring composition. There exists a tendency for the effect of preventing solvent from evaporating from a liquid droplet to fully exhibit by being more than the said lower limit.

The content of the dispersing vehicle 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 dispersant is usually 99% by mass. Also, considering the viscosity of the coloring composition suitable for coating, the lower limit of the content of the dispersant in the coloring composition is usually 70% by mass, preferably 75% by mass. The aforementioned dispersion medium can be used as a solvent for dissolving and removing precipitates formed in the coloring composition.

(Binder resin) The coloring composition of the present invention contains a binder resin (except for the aforementioned (a) block copolymer). Thereby, the alkaline developability of the coloring composition or the binding property on the substrate can be improved. Such a binder resin is not particularly limited, but is preferably a resin having an acidic group such as a carboxyl group or a phenolic hydroxyl group. The aforementioned binder resin can be, for example, an unsaturated monobasic acid added to at least a part of the epoxy group contained in the copolymer to a copolymer of an epoxy group-containing (meth)acrylate and other radically polymerizable monomers. The resulting resin, or the alkali-soluble resin obtained by adding polybasic acid anhydride to at least a part of the hydroxyl groups generated in the addition reaction; the linear alkali-soluble resin containing carboxyl groups in the main chain; Resins of unsaturated compounds of oxygen groups; (meth)acrylic resins; epoxy (meth)acrylate resins with carboxyl groups, etc. These can be used individually or in mixture of 2 or more types.

The aforementioned binder resin is preferably: a random copolymer containing structural units derived from carboxyl-containing vinyl monomers, structural units derived from (meth)acrylates, and styrene; A meth)acryl-based synthetic resin; and a random copolymer containing structural units derived from carboxyl-containing vinyl monomers and structural units derived from (meth)acrylate esters. The aforementioned carboxyl group-containing vinyl monomer is preferably (meth)acrylic acid. The aforementioned (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate , Phenoxyethyl (meth)acrylate, Cyclohexyl (meth)acrylate, Isobornyl (meth)acrylate, Adamantyl (meth)acrylate, Tricyclodecanyl (meth)acrylate, ( 2-Hydroxyethyl methacrylate, 4-Hydroxybutyl (meth)acrylate, Hydroxypropyl (meth)acrylate, Glycerin mono(meth)acrylate, Glycidyl (meth)acrylate, ( 3,4-epoxycyclohexylmethyl methacrylate, tetrahydrofurfuryl (meth)acrylate, etc.

In the aforementioned binder resin, the total content of structural units derived from carboxyl group-containing vinyl monomers and structural units derived from (meth)acrylates is preferably at least 50% by mass, more preferably 60% by mass above, and more preferably at least 70% by mass. In addition, in the aforementioned binder resin, the content rate of the structure derived from the carboxyl group-containing vinyl monomer is preferably at least 5% by mass, more preferably at least 10% by mass, still more preferably at least 20% by mass, and more preferably at least 20% by mass. It is 90 mass % or less, More preferably, it is 70 mass % or less.

Of these, random copolymers of carboxyl-containing vinyl monomers and (meth)acrylates are preferred. 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, (meth)acrylic acid Random copolymers with butyl (meth)acrylate and benzyl (meth)acrylate, etc. 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 carboxyl group-containing vinyl monomer and (meth)acrylic acid ester, the content of (meth)acrylic acid in the total monomer components is usually 5% by mass to 90% by mass, preferably 10% by mass to 70% by mass. % by mass, more preferably 20% by mass to 70% by mass.

The aforementioned binder resin may have a radically polymerizable carbon-carbon double bond in a side chain. By having a double bond in the side chain, the photocurability of the coloring composition of the present invention is improved, so resolution and adhesiveness can be further improved. The method of introducing a carbon-carbon double bond that can be radically polymerized in the side chain can be, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, ortho (or meta Or p) a method in which compounds such as vinyl benzyl glycidyl ether react with the acidic groups of the aforementioned binder resin.

The Mw of the binder resin is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, and still more preferably from 5,000 to 20,000. When the Mw of the binder resin is 3,000 or more, the heat resistance and film strength of the colored layer formed by the colored 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-170 mgKOH/g, more preferably 50 mgKOH/g-150 mgKOH/g, and more preferably 90 mgKOH/g-150 mgKOH/g. When the acid value of the binder resin is 20 mgKOH/g or more, the alkali developability when the coloring composition forms a colored layer is better, and when it is 170 mgKOH/g or less, the heat resistance is good.

Binder resin contained in a coloring composition may be only one type or plural types. In the coloring composition, the content of the binder resin is preferably from 5 parts by mass to 200 parts by mass, more preferably from 10 parts by mass to 100 parts by mass, and still more preferably from 20 parts by mass to 80 parts by mass, based on 100 parts by mass of the coloring material. share.

(crosslinking agent) The aforementioned coloring composition may contain a crosslinking agent. A crosslinking agent is a compound having two or more polymerizable groups. As a polymerizable group, an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, an N-alkoxymethylamino group etc. are mentioned, for example. The aforementioned crosslinking agent is preferably a compound having two or more (meth)acryl groups, or a compound having two or more N-alkoxymethylamino groups. The aforementioned crosslinking agents may be used alone or in combination of two or more.

Specific examples of the aforementioned compounds having two or more (meth)acryl groups include polyfunctional (meth)acrylates obtained by reacting aliphatic polyhydroxy compounds with (meth)acrylic acid, caprolactone-modified multifunctional Functional (meth)acrylate, alkylene oxide modified multifunctional (meth)acrylate, multifunctional urethane (meth)acrylic acid obtained by reacting hydroxyl-containing (meth)acrylate with multifunctional isocyanate Esters, polyfunctional (meth)acrylates with carboxyl groups obtained by reacting (meth)acrylates with hydroxyl groups with acid anhydrides, etc.

The aforementioned aliphatic polyols include, for example, divalent aliphatic polyols such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; Aliphatic polyols with more than three valences. The aforementioned hydroxyl-containing (meth)acrylates can be, for example, 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, neopentylthritol tri(meth)acrylate, di Neopentylthritol penta(meth)acrylate, diperythritol hexa(meth)acrylate, glycerin di(meth)acrylate, and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. The aforementioned acid anhydrides can be, for example, dibasic anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride; Anhydrides, diphenyl ketone tetracarboxylic dianhydrides and other tetrabasic acid dianhydrides.

In the colored composition of the present invention, the content of the crosslinking agent is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, relative to 100 parts by mass of the coloring material. When the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the amount of crosslinking is too large, the alkaline developability of the coloring composition of the present invention will decrease, and smearing and film residue will tend to occur on the unexposed substrate or the light-shielding layer.

(photopolymerization initiator) It is preferable that the said coloring composition contains a photoinitiator. Thereby, physical radiation property can be imparted to a coloring composition. The aforementioned photopolymerization initiator is a compound that generates active species that can initiate polymerization of the crosslinking agent by exposure to radiation such as visible light, ultraviolet rays, far infrared rays, electron rays, and X-rays.

The aforementioned photopolymerization initiators include, for example, thioxanthone-based compounds, acetophenone-based compounds, diimidazole-based compounds, triazine-based compounds, O-acyl oxime-based compounds, onium salt-based compounds, benzoin-based compounds, diphenyl Ketone-based compounds, α-diketone-based compounds, polynuclear quinone-based compounds, diazo-based compounds, imide sulfonate-based compounds, etc. A photopolymerization initiator can be used individually or in mixture of 2 or more types.

In the colored composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, relative to 100 parts by mass of the crosslinking agent. At this time, if the content of the photopolymerization initiator is too small, exposure curing may be insufficient, and on the other hand, if it is too large, the formed colored layer tends to be easily peeled off from the substrate during development.

(other admixtures) In addition to the above-mentioned compounding agent, other compounding agents may be compounded in the said coloring composition in the range which does not impair the preferable physical property of this invention. Other compounding agents include sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, plasticizers, organic carboxylic acid compounds, organic Carboxylic anhydrides, pH adjusters, antioxidants other than the aforementioned phenolic antioxidants, ultraviolet absorbers, light stabilizers, preservatives, antifungal agents, anti-aggregation agents, adhesion improvers, development improvers, storage stabilizers, etc. .

Sensitizing pigments include 4,4'-dimethylaminodiphenyl ketone, 4,4'-diethylaminodiphenyl ketone, 2-aminodiphenyl ketone, 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-diethylaminophenyl) Methylaminophenyl) benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl) 1,3,4-oxazole, 2-(p-dimethylaminophenyl base) 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-diethylaminophenyl) (methylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc.

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

Nonionic surfactants include fluorine-based 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-hexafluoropentyl) base) ether, octapropylene glycol bis (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol bis (1,1,2,2,3,3-hexafluoropentyl) ether, perfluorododecyl sodium alkylsulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc.) , Polysiloxane-based surfactants, polyoxyethylene-based surfactants (polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkanes Esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, neopentylthritol fatty acid esters, polyoxyethylene neopentylthritol fatty acid esters, sorbitan fatty acid esters, poly oxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc.) and the like.

Anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl Sulfates, higher alcohol sulfates, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphates, poly Oxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special polymer surfactants, etc. Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, alkylamine salts, and the like. Examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, amino acids, and the like.

Examples of plasticizers include dioctyl phthalate, bis(dodecyl) phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, triphosphate Cresyl ester, dioctyl adipate, dibutyl sebacate, triacetylglycerin, etc.

Examples of organic carboxylic acid compounds include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic 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, guananic acid, benzoin Carboxylic acid directly bonded to the carboxyl group of the phenyl group, such as acid and phthalic acid, and carboxylic acids bonded to the carboxyl group of the phenyl group through a carbon bond, etc.

Examples of organic carboxylic anhydrides 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, naphthalic anhydride, etc.

>Production method of coloring composition and color filter> A coloring composition can be prepared by mixing a dispersant composition, a coloring material, a dispersing vehicle, a binder resin, and optionally a crosslinking agent, a photopolymerization initiator, and other additives. In addition, (a) block copolymer, (b) aromatic compound, (c) tertiary amine compound, coloring material, dispersion medium, binder resin, and other components as needed can be mixed to prepare a coloring composition . For mixing, for example, a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, or a kneader can be used. The coloring composition is preferably filtered after mixing. Examples of other additives include pH adjusters, antioxidants, ultraviolet absorbers, photostabilizers, preservatives, antifungal agents, surfactants, anti-aggregation agents, and the like.

Since the said coloring composition has alkali developability, it is suitably used as a color filter.

The color filter of the present invention has a colored layer formed using the aforementioned colored composition. The manufacturing method of a color filter is, for example, the following method. First, thermally harden thermoplastic resin sheets such as polyester resins, polyolefin resins, polycarbonate resins, and polymethyl methacrylate resins, epoxy resins, unsaturated polyester resins, and poly(meth)acrylic resins. After coating, for example, the coloring composition of the present invention in which a red pigment is dispersed on transparent substrates such as transparent resin sheets and various glasses, prebaking is performed to evaporate the solvent (dispersion medium) to form a coating film. Next, after exposing the coating film through a photomask, it is developed with an alkaline developer (an aqueous solution containing an organic solvent or a surfactant and an alkaline compound, etc.) to dissolve and remove the unexposed portion of the coating film. Afterwards, a post-baking is performed to form a pixel array in which red pixel patterns are configured in a specific arrangement. Next, use the green coloring composition or the blue coloring composition, and carry out the coating, pre-baking, exposure, development and post-baking of each coloring composition in the same manner as above, and the green pixel array and the blue pixel array are sequentially formed on the same on the substrate. In this way, the color filter of red, green and blue three primary color pixel arrays can be arranged on the substrate. However, the order of forming pixels of each color in the present invention is not limited to the above.

When coating the coloring composition on the substrate, suitable coating methods such as spray method, roll coating method, spin coating method (spin coating), slot die coating method, bar coating method, etc. can be used, and spin coating method, slot coating method, etc. are especially preferred. Die coating method. After forming a protective film as needed on the pixel pattern thus obtained, a transparent conductive film (ITO etc.) is formed by sputtering. After the transparent conductive film is formed, a spacer can be further formed to become a color filter. In addition, a black matrix may also be provided on a transparent substrate used to form a pixel array of three primary colors of red, green and blue.

The color filter of the present invention has high dimensional accuracy 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. In addition, the viscosity of the coloring composition is low and the luminance of the coating film (coloring body) formed by the coloring composition is excellent, so it is suitable for use as a coloring column spacer. The coloring column spacer is supported by a TFT substrate sandwiching a liquid crystal layer and Color filter substrate. Examples include compositions with high optical density (Optical Depth: OD) described in JP-A-2015-191234. (Example)

The present invention will be further described in detail below according to specific embodiments. The present invention is not limited to the following examples, and appropriate changes can be made without changing the gist. 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 coloring composition were evaluated according to the following methods.

Also, the abbreviation refers to the following. BTEE: Ethyl-2-methyl-2-n-butyltelluryl-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 NOF 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: Phthalimidediazabicycloundecene. 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) measuring device (Bruker company make: AVANCE500 (frequency: 500 MHz)). From the obtained NMR spectrum, the peak integration ratio of the vinyl group derived from the monomer and the ester side chain derived from the polymer was calculated to calculate the polymerization rate of the monomer.

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

(amine value) The amine value is represented by the mass of potassium hydroxide (KOH) equivalent to the solid content per 1 g of the basic component. The measurement sample was dissolved in tetrahydrofuran, and the resulting solution was neutralized and titrated with a 0.1 mol/L hydrochloric acid/2-propanol solution using a potentiometric titration device (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). Use the inflection point of the titration pH curve as the end point of the titration, and calculate the amine value (B) with the following formula. B=56.11×Vs×0.1×f/w. B: Amine value (mgKOH/g). Vs: the amount of 0.1mol/L hydrochloric acid/2-propanol solution required for titration (mL). f: Power value of 0.1mol/L hydrochloric acid/2-propanol solution. w: Measurement sample mass (g) (solid content conversion).

(acid value) The acid value is represented by the mass of potassium hydroxide required to neutralize 1 g of acidic components in solid components. Dissolve the test sample in tetrahydrofuran, drop a few drops of phenolphthalein ethanol solution as indicator, and neutralize and titrate with 0.1mol/L potassium hydroxide/ethanol solution. The acid value (A) was calculated by the following formula. A=56.11×Vs×0.1×f/w. A: acid value (mgKOH/g). Vs: The amount of 0.1mol/L potassium hydroxide/ethanol solution required for titration (mL). f: Power value of 0.1mol/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 conical rotor (1°34'×R24) was used to measure the viscosity at 25° C. at a rotor speed of 60 rpm. After preparing the coloring composition and storing it at 25° C. for 2 hours, the viscosity was measured. Those with a viscosity of less than 10mPa･s were evaluated as "A", and those with a viscosity of 10mPa･s or more were evaluated as "B".

(Brightness) The colored composition was coated on a glass plate, dried, and then heat-treated at 230° C. for 30 minutes to form a coating film and produce colored glass. Set the colored glass plate in a spectrophotometer (trade name: CM-3700d, manufactured by KONICA MINOLTA SENSING Co., Ltd.), and measure the transmittance chromaticity of the XYZ coordinate axis in the C light source. The Y value at this time is adopted as the luminance (Y). In Table 2, regarding luminance, coloring compositions No. 1 to 8 were evaluated based on the luminance of a colored glass plate using coloring 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". In addition, coloring compositions No. 9 to 11 were evaluated based on the brightness of the colored glass plate using coloring 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. 0.2 is "A", and a difference of 0 is "B".

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

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

After the reaction was completed, methanol (165 g) previously replaced by argon was added to the reaction solution to dilute it, 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 in the copolymer was 63% by mass, and the B block content was 37% by mass , The content rate of the structural unit derived from the vinyl monomer having an acidic group in the copolymer is 4.3% by mass, the total of the structural unit represented by the general formula (1) and the general formula (2) in the copolymer The content rate is 36.0 mass %. Also, the content rate of each structural unit in the copolymer was calculated from the addition rate of the vinyl monomer used in the polymerization reaction, the polymerization rate of the vinyl monomer, and the reaction rate of the quaternization agent used in the quaternization reaction.

>Preparation of dispersant composition> (Dispersant composition No.A) 87.5 g of block copolymers, 8.91 g of PI, 9.23 g of DBU, 110 g of PMA, and 110 g of MP were added to a flask equipped with a stirrer, and 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 No.B~H was obtained in the same manner as the preparation method of the dispersant composition No.A.

【Table 1】

> Modulation of coloring composition > (Coloring composition No.1) 18 parts by mass of a pigment (C.I. 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 ( Product name: Ripoxy (registered trademark) SPC-2000, Showa Polymer Co., Ltd.) 5.4 parts by mass, and 64.6 parts by mass of PMA were stirred at 2000 rpm for 10 minutes using a disperser to perform preliminary dispersion. 640 parts by mass of zirconia beads with a diameter of 0.5 mm were added to the obtained preliminary dispersion, and stirred at 2000 rpm for 2 hours to perform full-scale dispersion. 28.5 parts by mass of PMA were added to the obtained dispersion, and further stirred at 1500 rpm for 10 minutes. The resulting final dispersion was filtered through a 2.5 μm mesh filter (trade name: HDC II Membrene Filler, manufactured by PALL Corporation) to remove the zirconia beads. The viscosity and brightness of the obtained coloring composition were evaluated. The results are shown in Table 2.

(Coloring composition No.2~8) Coloring compositions No. 2 to 8 were prepared in the same manner as the preparation method of coloring composition No. 1 except that the dispersant was changed to those shown in Table 2. In coloring composition No. 8, the block copolymer obtained above was used as a dispersant.

(coloring composition No.9) 16 parts by mass of a pigment (C.I. Pigment Blue 15:6, trade name: FASTGEN (registered trademark) Blue A540, manufactured by DIC Corporation), 24 parts by mass of a dispersant composition, and alkali-soluble binder resin were put into a mixing tank with an internal capacity of 500 ml. 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 stirred at 2000 rpm for 10 minutes using a disperser to perform preliminary dispersion. 640 parts by mass of zirconia beads with a diameter of 0.5 mm were 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 were added to the obtained dispersion, and further stirred at 1500 rpm for 10 minutes. The resulting final dispersion was filtered through a 2.5 μm mesh filter (trade name: HDC II Membrene Filler, manufactured by PALL Corporation) to remove the zirconia beads. The viscosity and brightness of the obtained coloring composition were evaluated. The results are shown in Table 2.

(Colored Compositions 10-11) Colored Compositions No. 10 and 11 were prepared in the same manner as that of Colored Composition No. 9, except that the dispersant was changed as shown in Table 2. In coloring composition No. 11, the block copolymer obtained above was used as a dispersant. 【Table 2】

Dispersants Use dispersant compositions No.A~H for coloring compositions No. 1~7, 9, and 10, which have high pigment dispersibility and low viscosity. Among them, dispersant composition Nos.A~E and H contain a cyclic amidine compound as a tertiary amine compound, and coloring composition Nos. 1~5, 9 using the dispersant composition No.A~E and H , 10 The brightness of the coating film is also excellent. That is, coloring composition Nos. 1 to 5, 9, and 10 have excellent discoloration resistance even when exposed to high temperature in the process of manufacturing a liquid crystal display, and when color filters are produced using these coloring compositions, an increase in luminance can be expected.

The following embodiments are included in the present invention. (implementation mode 1) A dispersant composition, which is formed by mixing (a), (b) and (c), (a) block copolymer, which has A block and B block, and the A block contains acidic The structural unit of the vinyl monomer of the group, the B block contains the structural unit shown in the following general formula (1) and the structural unit shown in the following general formula (2); (b) is composed of aromatic dicarboxylic acid amide At least one aromatic compound selected from the group consisting of amines, acidic group-containing aromatic compounds, and phenolic hydroxyl-containing aromatic compounds; (c) tertiary amine compounds.

〔式(1)中，R¹¹ 、R¹² 及R¹³ 分別獨立表示可具有取代基之鏈狀或環狀之烴基。R¹¹ 、R¹² 及R¹³ 中兩個以上可互相鍵結形成環狀構造。X¹ 表示二價連結基。R¹⁴ 表示氫原子或甲基。Y^- 表示對離子。〕[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 ^- indicates a counter ion. 〕

〔式(2)中，R²¹ 及R²² 分別獨立表示可具有取代基之鏈狀或環狀之烴基。R²¹ 及R²² 可互相鍵結形成環狀構造。X² 表示二價連結基。R²³ 表示氫原子或甲基。〕[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. 〕

(implementation mode 2) The dispersant composition as described in Embodiment 1, wherein the molar ratio of the quaternary ammonium salt group in the aforementioned (a) block copolymer to the aforementioned (b) aromatic compound ((b)/(a) The quaternary ammonium base) is 0.5~1.2.

(implementation mode 3) The dispersant composition as described in Embodiment 1 or 2, wherein the molar ratio ((c)/( The quaternary ammonium base in a) is 0.5~1.2.

(implementation mode 4) The dispersant composition as described in any one of Embodiments 1 to 3, wherein in the aforementioned (a) block copolymer, the content rate of the structural unit derived from the vinyl monomer having an acidic group is 1 mass %~20% by mass.

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

(implementation form 6) The dispersant composition described in any one of Embodiments 1 to 5, wherein the aforementioned (c) tertiary amine compound is a compound represented by general formula (6) and/or a compound represented by general formula (7).

〔通式(6)中，R⁶¹ 、R⁶² 及R⁶³ 分別獨立表示可具有取代基之碳數1~10之烴基。又，R⁶² 及R⁶³ 可互相鍵結形成環狀構造。〕[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. In addition, R ⁶² and R ⁶³ may be bonded to each other to form a ring structure. 〕

〔通式(7)中，R⁷¹ 表示可具有取代基之碳數2~6之二價烴基，R⁷² 及R⁷³ 分別獨立表示氫原子或可具有取代基之碳數1~10之烴基。又，R⁷² 及R⁷³ 可互相鍵結形成環狀構造。〕[chemical formula 22]

[In the general formula (7), R ⁷¹ represents a divalent hydrocarbon group with 2 to 6 carbon atoms that may have a substituent, and R ⁷² and R ⁷³ independently represent a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms that may have a substituent. In addition, R ⁷² and R ⁷³ may be bonded to each other to form a ring structure. 〕

(implementation mode 7) A coloring composition containing the dispersing agent composition described in any one of Embodiments 1 to 6, a coloring material, a dispersing vehicle, and a binder resin.

(implementation pattern 8) A coloring composition, which is made by mixing (a), (b), (c), coloring material, dispersing medium and binder resin, (a) block copolymer, which has A block and B block, the The A block contains a structural unit derived from a vinyl monomer with an acidic group, and the B block contains a structural unit shown in the following general formula (1) and a structural unit shown in the following general formula (2); (b ) At least one aromatic compound selected from the group consisting of aromatic dicarboxylic acid imides, acidic group-containing aromatic compounds, and phenolic hydroxyl-containing aromatic compounds; (c) tertiary amine compounds.

〔式(1)中，R¹¹ 、R¹² 及R¹³ 分別獨立表示可具有取代基之鏈狀或環狀之烴基。R¹¹ 、R¹² 及R¹³ 中兩個以上可互相鍵結形成環狀構造。X¹ 表示二價連結基。R¹⁴ 表示氫原子或甲基。Y^- 表示對離子。〕[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 ^- indicates a counter ion. 〕

〔式(2)中，R²¹ 及R²² 分別獨立表示可具有取代基之鏈狀或環狀之烴基。R²¹ 及R²² 可互相鍵結形成環狀構造。X² 表示二價連結基。R²³ 表示氫原子或甲基。〕[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. 〕

(implementation form 9) The coloring composition as described in Embodiment 7 or 8, wherein the aforementioned coloring material is a phthalocyanine pigment.

(implementation form 10) The coloring composition described in any one of Embodiments 7 to 9 is used for a color filter.

(implementation form 11) A color filter including a colored layer formed using the colored composition described in Embodiment 10. (Industrial Utilization)

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

Claims (11)

A dispersant composition, which is formed by mixing (a), (b), and (c), (a) a block copolymer, which has an A block and a B block, and the aforementioned A block contains The structural unit of the vinyl monomer of the acidic group, the aforementioned B block contains the structural unit shown in the following general formula (1) and the structural unit shown in the following general formula (2); (b) is composed of aromatic dicarboxylic acid amide At least one aromatic compound selected from the group consisting of imines, aromatic compounds containing acidic groups, and aromatic compounds containing phenolic hydroxyl groups; (c) tertiary amine compounds; wherein, the structure shown in general formula (1) The unit content is 30% by mass to 85% by mass in 100% by mass of the B block, and the content of the structural unit represented by the general formula (2) is 15% by mass in 100% by mass of the B block More than 70% by mass;

[In formula (1), R ¹¹ , R ¹² and R ¹³ independently represent chain or cyclic hydrocarbon groups that may have substituents, and two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a cyclic structure, X ¹ represents a divalent linking group, R ¹⁴ represents a hydrogen atom or a methyl group, Y ^- represents a counter ion] [Chemical Formula 2]

[In formula (2), R ²¹ and R ²² independently represent a chain or cyclic hydrocarbon group that may have a substituent, R ²¹ and R ²² can 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]. The dispersant composition as described in Claim 1, wherein the molar ratio of the quaternary ammonium base in the aforementioned (a) block copolymer to the aforementioned (b) aromatic compound ((b)/(a) Quaternary ammonium base) is 0.5~1.2. The dispersant composition as described in Claim 1, wherein the molar ratio of the quaternary ammonium base in the aforementioned (a) block copolymer to the aforementioned (c) tertiary amine compound ((c)/(a) The quaternary ammonium base) is 0.5~1.2. The dispersant composition as described in claim 1, wherein in the (a) block copolymer, the content of the structural unit derived from the vinyl monomer having an acidic group is 1% by mass to 20% by mass. The dispersant composition as described in Claim 1, wherein in the aforementioned (a) block copolymer, the total content rate of the structural unit represented by the aforementioned general formula (1) and the aforementioned structural unit represented by the aforementioned general formula (2) is 5 Mass%~50 mass%. The dispersant composition as described in any one of claims 1 to 5, wherein the aforementioned (c) tertiary amine compound is a compound represented by general formula (6) and/or a compound represented by general formula (7),

[In the general formula (6), R ⁶¹ , R ⁶² and R ⁶³ independently represent a hydrocarbon group with 1 to 10 carbon atoms that may have a substituent, and R ⁶² and R ⁶³ may be bonded to each other to form a ring structure]

[In the general formula (7), R ⁷¹ represents a divalent hydrocarbon group with a carbon number of 2 to 6 that may have a substituent, R ⁷² and R ⁷³ independently represent a hydrogen atom or a hydrocarbon group with a carbon number of 1 to 10 that may have a substituent, R ⁷² and R ⁷³ can bond with each other to form a ring structure]. The dispersant composition as described in Claim 6, wherein the compound represented by the aforementioned general formula (6) is selected from trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, and triisopropylamine as aliphatic amines , tributylamine, N-methyl-diethylamine, N-ethyldiamylamine; N,N-dimethylaniline, N,N-diethylaniline as aromatic amines; as alicyclic amines The group consisting of N,N-dimethyl-cyclohexylamine and N,N-diethyl-cyclohexylamine; the compound represented by the aforementioned general formula (7) is represented by the following general formula (8) Cyclic amidine compounds;

[In the general formula (8), ^R80 ~ ^R89 independently represent a hydrogen atom, an alkyl group with 1~10 carbons, an aryl group with 6~10 carbons, n is an integer of 1~4, m is 1~4 Integer of ]. A colored composition containing the dispersant composition described in any one of Claims 1 to 7, a coloring material, a dispersing vehicle, and a binder resin. The coloring composition as described in claim 8, wherein the coloring material is a phthalocyanine pigment. The coloring composition as described in Claim 9 is used for color filters. A color filter comprising a colored layer formed using the colored composition described in claim 10.