KR20210002470A - Dispersant composition, coloring composition and color filter - Google Patents

Abstract

[식 (1), (2)에 있어서, R¹¹, R¹², R¹³, R²¹ 및 R²²는, 각각 독립적으로, 치환기를 갖고 있어도 되는 쇄상 혹은 환상의 탄화수소기를 나타낸다. R¹¹, R¹² 및 R¹³ 중 2개 이상이 서로 결합하여 환상 구조를 형성하고 있어도 된다. R²¹ 및 R²²가 서로 결합하여 환상 구조를 형성하고 있어도 된다. R¹⁴, R²³은 수소 원자 또는 메틸기를 나타낸다. X¹, X²는 2가의 연결기를 나타낸다. Y^-는 상대 이온을 나타낸다.](Problem) An object of the present invention is to provide a dispersant composition having excellent pigment dispersibility.
(Solution means) The dispersant composition comprises: (a) a block copolymer having an A block having an acidic group and a B block containing structural units represented by the general formulas (1) and (2); (b) aromatic compounds; (c) It is characterized by mixing a tertiary amine compound.

[In formulas (1) and (2), R ¹¹ , R ¹² , R ¹³ , R ²¹ and R ²² 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 cyclic structure. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. R ¹⁴ and R ²³ represent a hydrogen atom or a methyl group. X ¹ and X ² represent a divalent linking group. Y ^- represents a counter ion.]

Description

Dispersant composition, coloring composition and color filter

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

Conventionally, in manufacturing a color filter used in a liquid crystal display or the like, as a method of imparting a coloring material to a substrate, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like are known. Among these, from the viewpoints of spectral characteristics, durability, pattern shape, and precision, the pigment dispersion method is widely used. In the pigment dispersion method, for example, a coating film made of a coloring composition in which a pigment, a dispersant, a dispersion medium (solvent), and the like are mixed is formed on a substrate, exposed through a photomask having a desired pattern shape, and alkali development is performed. All.

Recently, for color filters, higher transmission, higher luminance, higher contrast, and higher color gamut are required. Therefore, various studies have been conducted, such as increasing the concentration of the pigment in the colored composition, and the development of a pigment whose intrinsic transmission and absorption spectrum matches the phosphor spectrum of the backlight.

In particular, with regard to increasing the luminance of green pixels, a new halogenated zinc phthalocyanine green pigment having a specific color as described in Patent Documents 1 and 2, for example, has been proposed. Thereby, high luminance for the conventional halogenated copper phthalocyanine green pigment has been realized. In addition, Patent Document 3 includes a structural unit derived from a vinyl monomer having a tertiary amino group and a structural unit derived from a vinyl monomer having a quaternary ammonium base, and the content ratio of the quaternary ammonium base is a tertiary amino group and a quaternary ammonium salt. It is disclosed to use a dispersing agent of 60 mol% or less of the total content of groups.

Japanese Patent Publication No. 2004-70342 Japanese Patent Publication No. 2004-70343 Japanese Patent Publication No. 2016-38584

However, when the pigment described in Patent Documents 1 and 2 is used, the viscosity of the pigment dispersion is increased, and it becomes difficult to industrially manufacture a colored resin composition using this pigment dispersion. Moreover, in the dispersing agent used by the method of patent document 3, the pigment dispersibility was not sufficient. The present invention has been made in view of the above circumstances, and an object thereof is to provide a dispersant composition having excellent pigment dispersibility.

The dispersant composition of the present invention capable of solving the above problems includes (a) a block A containing a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the following general formula (1), and the following general formula (2) A block copolymer having a B block containing a structural unit represented by ), (b) at least one aromatic compound selected from the group consisting of an aromatic dicarboxylic acid imide, an acidic group-containing aromatic compound, and a phenolic hydroxy group-containing aromatic compound , And, (c) a tertiary amine compound is mixed.

[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 cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion.]

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

When the dispersant composition of the present invention is used, a coloring composition having a high dispersibility of the coloring material and a low viscosity is obtained. In particular, when a cyclic amidine compound is used as the (c) tertiary amine compound, the luminance of the coating film formed from the colored composition can also be improved.

The dispersant composition of the present invention comprises (a) a block A containing a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the general formula (1) described later, and the general formula (2) described later. A block copolymer having a B block containing a structural unit; (b) at least one aromatic compound selected from the group consisting of an aromatic dicarboxylic acid imide, an acidic group-containing aromatic compound, and a phenolic hydroxy group-containing aromatic compound; (c) It is characterized by mixing a tertiary amine compound.

(a) block copolymer

The dispersant composition contains (a) a block copolymer. Only one type of the block copolymer (a) may be used in combination, or two or more types may be used in combination. The block copolymer (a) includes a block A containing a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the general formula (1) described later, and a structure represented by the general formula (2) described later. It has a B block containing units.

In the present invention, "A block" can be referred to as "A segment", and "B block" can be referred to as "B segment". In the present invention, the "vinyl monomer" refers to a monomer having a carbon-carbon double bond capable of radical polymerization in a molecule. "Structural unit derived from a vinyl monomer" refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a vinyl monomer is polymerized to form a single carbon-carbon bond. "(Meth)acrylic" means "at least one of acrylic and methacryl." "(Meth)acrylate" means "at least one of an acrylate and a methacrylate". "(Meth)acryloyl" means "at least one of acryloyl and methacryloyl".

(A block)

The A block is a polymer block having a structural unit derived from a vinyl monomer having an acidic group. It is believed that the A block facilitates alkali development by having an acidic group. Therefore, the block copolymer can be suitably used for a color composition for color filters used in the production of a color filter employing alkali development.

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

As the vinyl monomer having an acidic group, at least one selected from a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, or a vinyl monomer having a phosphoric acid group is preferable. Among these, preferably, at least one selected from (meth)acryl monomers having a carboxyl group, (meth)acryl monomers having a sulfonic acid group, or (meth)acrylic monomers having a phosphoric acid group.

Examples of the vinyl monomer having a carboxyl group include (meth)acrylic acid; Vinyl monomers having a hydroxy group such as 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, and 2-(meth)acryloyloxyethylphthalate (preferably hydroxy Monomers obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride and phthalic anhydride with alkyl (meth)acrylate); Crotonic acid; Maleic acid; Itaconic acid, etc. are mentioned.

Examples of the vinyl monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, ethyl disulfonic acid (meth)acrylate, methylpropylsulfonic acid (meth)acrylamide, and ethyl sulfonic acid (meth)acrylamide.

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

The content rate of the structural unit derived from a vinyl monomer having an acidic group is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and 20% by mass in 100% by mass of the A block. % Or less is preferable, more preferably 18% by mass or less, and still more preferably 16% by mass or less. When the content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate when neutralized with alkali is accelerated in the alkali phenomenon, and when it is 20% by mass or less, the hydrophilicity is not too high, and the formed pixel is messy. You can suppress the loss.

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

Specific examples of vinyl monomers capable of forming other structural units of the A block include α-olefins, aromatic vinyl monomers, vinyl monomers containing heterocycles, vinylamides, vinyl carboxylate, dienes, and (meth)acryl monomers. I can. These vinyl monomers may have a hydroxy group and an epoxy group.

As an α-olefin, 1-hexene, 1-octene, 1-decene, etc. are mentioned.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, and 1-vinylnaphthalene.

Examples of the vinyl monomer containing a hetero ring include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 2-vinylpyridine, 4-vinylpyridine, and the like.

Examples of the vinylamide include N-vinylformamide, N-vinylacetamide, 1-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam.

As vinyl carboxylate, vinyl acetate, vinyl pivalate, vinyl benzoate, etc. are mentioned.

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

Examples of the (meth)acryl monomer include (meth)acrylates having a chain alkyl group (linear alkyl group or branched chain alkyl group); (Meth)acrylate having a cyclic alkyl group (monocyclic structure); (Meth)acrylate having an aromatic ring group; (Meth)acrylamide; (Meth)acrylate having a polyalkylene glycol structural unit; (Meth)acrylate having a hydroxy group; (Meth)acrylate having a lactone-modified hydroxy group; (Meth)acrylate having an alkoxy group; (Meth)acrylate etc. which have a cyclic ether group are mentioned.

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

Examples of (meth)acrylamide include (meth)acrylamide, N-methyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, and the like.

Examples of the (meth)acrylate having a polyalkylene glycol structural unit include polyethylene glycol (degree of polymerization = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization = 2 to 10) ethyl ether (meth) acrylate, polyethylene (Meth)acrylate having a polyethylene glycol structural unit such as glycol (degree of polymerization = 2 to 10) propyl ether (meth) acrylate and polyethylene glycol (degree of polymerization = 2 to 10) phenyl ether (meth) acrylate; Polypropylene glycol (degree of polymerization = 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 2 to 10) ethyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 2 to 10) propyl ether (meth) ) Acrylate, polypropylene glycol (polymerization degree = 2 to 10), and (meth)acrylates having a polypropylene glycol structural unit such as phenyl ether (meth)acrylate.

Examples of the (meth)acrylate having a hydroxy group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. ) Hydroxyalkyl (meth)acrylates, such as an acrylate, etc. are mentioned.

Examples of the (meth)acrylate having a lactone-modified hydroxy group include those obtained by adding lactone to the (meth)acrylate having a hydroxy group, and those obtained by adding caprolactone are preferable. The amount of lactone added is preferably 1 mol to 10 mol, more preferably 1 mol to 5 mol. Examples of the lactone-modified hydroxy group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate with 1 mol of caprolactone adduct, 2-hydroxyethyl (meth)acrylate with 2 mol of caprolactone adduct, and 2-hydroxy Caprolactone 3 mol adduct of oxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate caprolactone 4 mol adduct, 2-hydroxyethyl (meth)acrylate caprolactone 5 mol adduct, 2- And a 10 mol adduct of caprolactone of hydroxyethyl (meth)acrylate.

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

As the (meth)acrylate having a cyclic ether group, glycidyl (meth)acrylate, (meth)acrylic acid tetrahydrofurfuryl, (meth)acryloylmorpholine, (meth)acrylic acid 2-(4-morpholinyl) )Ethyl, (3-ethyloxetan-3-yl)methyl(meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl(meth)acrylate, cyclic trimethyl All propane formal (meth)acrylate, 2-[(2-tetrahydropyranyl)oxy]ethyl (meth)acrylate, 1,3-dioxane-(meth)acrylate, etc. are mentioned.

Vinyl monomers capable of forming other structural units that may be included in block A are preferably (meth)acryl monomers, and (meth)acrylates having a chain alkyl group, (meth)acrylates having an aromatic ring group, and polyalkylene At least one selected from the group consisting of (meth)acrylate having a glycol structural unit, (meth)acrylate having a hydroxy group, (meth)acrylate having a lactone-modified hydroxy group, and (meth)acrylate having a cyclic ether group More preferable. The vinyl monomers that can be used as A block may be used in one or two or more types, respectively.

A block is derived from at least one vinyl monomer selected from the group consisting of (meth)acrylate having a chain alkyl group, (meth)acrylate having a cyclic alkyl group, and (meth)acrylate having an aromatic cyclic group. In the case of having a structural unit, the total content of these structural units is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, even more preferably in 100% by mass of the A block. Is 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, and 98% by mass or less is preferable, more preferably 95% by mass or less, still more preferably 90% by mass Below.

Block A is (meth)acrylamide, (meth)acrylate having a polyalkylene glycol structural unit, (meth)acrylate having a hydroxy group, (meth)acrylate having a lactone-modified hydroxyl group, (meth) having an alkoxy group In the case of having a structural unit derived from at least one vinyl monomer selected from the group consisting of acrylate and (meth)acrylate having a cyclic ether group, the total content of these structural units is in 100% by mass of A block. 2% by mass or more is preferable, more preferably 5% by mass or more, still more preferably 10% by mass or more, and 70% by mass or less is preferable, more preferably 65% by mass or less, still more preferably 60% by mass % Or less, still more preferably 50 mass% or less, still more preferably 30 mass% or less, particularly preferably 20 mass% or less.

Moreover, it is preferable that the A block does not have an amino group. That is, it is preferred that the vinyl monomer constituting the A block does not contain a vinyl monomer having an amino group. When a large amount of amino groups are present in the A block, when used as a dispersant for the coloring material, the coloring material is adsorbed to both the A block and the B block, and the dispersing performance of the coloring material is lowered. The content rate of the structural unit derived from the vinyl monomer having an amino group in the A block is preferably 2% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, most preferably 0% by mass to be.

When two or more types of structural units are contained in the A block, various structural units contained in the A block may be contained in any of random copolymerization, block copolymerization, etc. in the A block, and random copolymerization from the viewpoint of uniformity It is preferably contained in the form of. For example, the A block may be formed of a copolymer of a structural unit composed of an a1 block and a structural unit composed of an a2 block.

(B block)

The B block is a polymer block having a structural unit represented by general formula (1) and a structural unit represented by general formula (2). The B block is considered to have a high affinity with a coloring material since it has a quaternary ammonium base in addition to a tertiary amino group.

(Structural unit represented by general formula (1))

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

[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 cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion.]

The chain hydrocarbon group represented by R ¹¹ to R ¹³ includes both linear and branched chains. Examples of the substituents of the chain hydrocarbon group represented by R ¹¹ to R ¹³ include a halogen group, an alkoxy group, a benzoyl group (-COC ₆ H ₅ ), and a hydroxy group. Examples of the substituents of the cyclic hydrocarbon group represented by R ¹¹ to R ¹³ include a chain alkyl group, a halogen atom, an alkoxy group, and a hydroxy group.

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

Examples of the cyclic structure formed by bonding of two or more of R ¹¹ to R ¹³ to each other include a 5- to 7-membered nitrogen-containing heteromonocyclic ring or a condensed ring formed by condensing two or more of them. It is preferable that the nitrogen-containing heterocycle does not have aromaticity, and a saturated ring is more preferable. Specifically, structures represented by the following formulas (1-1), (1-2), and (1-3) are exemplified.

[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 the integer of 0-5. m represents the integer of 0-4. n represents the integer of 0-4. * Represents the number of bonds. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ¹⁶ may be the same or different.]

In the general formula (1), as the divalent linking group X ¹ , for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, -CONH-R ¹⁷ -group (amide group), -COO-R ¹⁸ -group ( Ester group) and the like, preferably a -CONH-R ¹⁷ -group and/or a -COO-R ¹⁸ -group, more preferably a -COO-R ¹⁸ -group. In addition, although the bonding direction of the amide group and the ester group is not particularly limited, C-CO-NH-R ¹⁷ -N ⁺ R ¹¹ R ¹² R ¹³ is preferable as the bonding aspect of the amide group, and C -CO-OR ¹⁸ -N ⁺ R ¹¹ R ¹² R ¹³ is preferred.

R ¹⁷ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms It is an alkylene group of 4. As a specific example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, etc. are mentioned.

R ¹⁸ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms It is an alkylene group of 4. As a specific example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, etc. are mentioned.

Examples of Y ⁻ include halogen anion, carboxylate anion, nitroxide anion, sulfate anion, sulfonate anion, and phosphate anion.

Examples of the halogen anion include fluoro anion, chloro anion, bromo anion, and iodine anion.

Examples of the carboxylate anion include alkyl carboxylate anions such as acetate anion and propionic acid anion; And aromatic carboxylate anions such as benzoate anions.

Examples of the sulfate anion include alkyl sulfate anions such as methyl sulfate anion and ethyl sulfate anion; And aromatic sulfate anions such as phenyl sulfate anion and benzyl sulfate anion.

Examples of the sulfonate anion include alkylsulfonate anions such as methanesulfonic acid anion and ethanesulfonic acid anion; And aromatic sulfonate anions such as benzenesulfonic acid anions and toluenesulfonic acid anions.

Examples of the phosphate anion include alkyl phosphate anions such as methyl phosphate anion; And aromatic phosphate anions such as phenyl phosphate anions.

Specific examples of the vinyl monomer forming the structural unit represented by the above formula (1) include (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxypropyltrimethylammonium chloride, and (meth)acryloyloxy Butyltrimethylammonium chloride, (meth)acryloyloxyethylbenzyldimethylammonium chloride, (meth)acryloyloxypropylbenzyldimethylammonium chloride, (meth)acryloyloxybutylbenzyldimethylammonium chloride, (meth)acryloyl Oxyethylbenzyldiethylammonium chloride, (meth)acryloyloxypropylbenzyldiethylammonium chloride, (meth)acryloyloxybutylbenzyldiethylammonium chloride, (meth)acryloylamidepropylbenzyldimethylammonium chloride, ( Meth)acryloyloxyethyltrimethylammonium bromide, (meth)acryloyloxypropyltrimethylammonium bromide, (meth)acryloyloxybutyltrimethylammonium bromide, (meth)acryloyloxyethylbenzyldimethylammonium bromide, (meth) )Acryloyloxypropylbenzyldimethylammonium bromide, (meth)acryloyloxybutylbenzyldimethylammonium bromide, (meth)acryloyloxyethylbenzyldiethylammonium bromide, (meth)acryloyloxypropylbenzyldiethylammonium Bromide, (meth)acryloyloxybutylbenzyldiethylammonium bromide, (meth)acryloylamidepropylbenzyldimethylammonium bromide, (meth)acryloyloxyethyltrimethylammonium iodide, (meth)acryloyloxy Propyltrimethylammonium iodide, (meth)acryloyloxybutyltrimethylammonium iodide, (meth)acryloyloxyethylbenzyldimethylammonium iodide, (meth)acryloyloxypropylbenzyldimethylammonium iodide , (Meth)acryloyloxybutylbenzyldimethylammonium iodide, (meth)acryloyloxyethylbenzyldiethylammonium iodide, (meth)acryloyloxypropylbenzyldiethylammonium iodide, (meth) )Acryloyloxybutylbenzyldiethylammonium iodide, (meth)acryloyloxyethyltrimethylammonium fluoride, (meth)acryloyloxypropyltrimethylammonium fluoride, (meth)acryloyloxybutyltrimethylammonium Fluoride, (meth)acryloyloxyethylbenzyldimethylammonium fluoride, (meth)acryloyloxypropylbenzyldimethylammonium fluoride De, (meth)acryloyloxybutylbenzyldimethylammonium fluoride, (meth)acryloyloxyethylbenzyldiethylammonium fluoride, (meth)acryloyloxypropylbenzyldiethylammonium fluoride, (meth)acrylic Royloxybutylbenzyldiethylammonium fluoride, (meth)acryloyloxyethyltrimethylammonium = methylsulfite, (meth)acryloyloxypropyltrimethylammonium = methylsulfite, (meth)acryloyloxybutyltrimethyl Ammonium=methylsulfite, (meth)acryloyloxyethyldimethylethylammonium=ethylsulfite, (meth)acryloyloxypropyldimethylethylammonium=ethylsulfite, (meth)acryloyloxybutyldimethylethylammonium= Ethyl sulfite, (meth)acryloyloxyethyltrimethylammonium=toluene-4-sulfonate, (meth)acryloyloxypropyltrimethylammonium=toluene-4-sulfonate, (meth)acryloyloxybutyltrimethylammonium =toluene-4-sulfonate, (meth)acryloylamide propyltrimethylammonium = methyl sulfite, (meth)acryloylamide propylethyldimethylammonium = ethyl sulfite, and the like.

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

(Structural unit represented by general formula (2))

The structural unit represented by General Formula (2) has a tertiary amine structure. The structural unit represented by the general formula (2) in the B block may be only one type or may have two or more types.

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

Both linear and branched chains are contained in the chain hydrocarbon group represented by R ²¹ or R ²² . Examples of the substituents of the chain hydrocarbon group represented by R ²¹ or R ²² include a halogen group, an alkoxy group, a benzoyl group, and a hydroxy group. Examples of the substituents of the cyclic hydrocarbon group represented by R ²¹ or R ²² include a chain alkyl group, a halogen group, an alkoxy group, and a hydroxy group.

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

Examples of the cyclic structure formed by bonding of R ²¹ or R ²² to each other include a 5- to 7-membered nitrogen-containing heteromonocyclic ring or a condensed ring formed by condensing two of them. It is preferable that the nitrogen-containing heterocycle does not have aromaticity, and a saturated ring is more preferable. Specifically, structures represented by the following formulas (2-1), (2-2), and (2-3) are exemplified.

[In General Formulas (2-1), (2-2), and (2-3), R ²⁴ represents an alkyl group having 1 to 6 carbon atoms. l represents the integer of 0-5. m represents the integer of 0-4. n represents the integer of 0-4. * Represents the number of bonds. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ²⁴ may be the same or different.]

In the general formula (2), as the divalent linking group X ² , for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, -CONH-R ²⁵ -group (amide group), -COO-R ²⁶ -group (Ester group) etc. are mentioned, Preferably it is -COO-R ²⁶ -group and/or -CONH-R ²⁵ -group, Preferably -CONH-R ²⁵ -group and/or -COO-R ²⁶ It is a-group, More preferably, it is a -COO-R ²⁶ -group. In addition, the bonding direction of the amide group and the ester group is not particularly limited, but the bonding aspect of the amide group is preferably C-CO-NH-R ²⁵ -NR ²¹ R ²² , and the bonding aspect of the ester group is C-CO- OR ²⁶ -NR ²¹ R ²² is preferred.

R ²⁵ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms It is an alkylene group of 4. As a specific example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, etc. are mentioned.

R ²⁶ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms It is an alkylene group of 4. As a specific example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, etc. are mentioned.

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

The B block may be only a structural unit represented by general formula (1) and a structural unit represented by general formula (2), or may contain other structural units. From the viewpoint of maintaining the affinity with the coloring material, the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the B block is preferably 80% by mass or more, and more Preferably it is 90 mass% or more, More preferably, it is 95 mass% or more. In addition, it is preferable that the B block 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 having an acidic group is preferably 5% by mass or less, and more preferably 3% by mass or less in 100% by mass of the B block.

Specific examples of the vinyl monomer capable of forming the other structural units of the B block include the same ones exemplified as the specific examples of the vinyl monomer capable of forming the other structural units of the A block.

When two or more types of structural units are contained in the B block, various structural units contained in the B block may be contained in any of random copolymerization, block copolymerization, etc. in the B block, and random copolymerization from the viewpoint of uniformity It is preferably contained in the form of. For example, the B block may be formed of a copolymer of a structural unit composed of a b1 block and a structural unit composed of a b2 block.

(Block copolymer)

The structure of the 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, when the A block is expressed as A and the B block is B, (AB) _m- type , (AB) _m -A type, (BA) _m -B type (m is an integer greater than or equal to 1, for example, it is preferably a copolymer having at least one structure selected from the group consisting of 1 to 3) . Among these, it is preferable that it is a diblock copolymer represented by AB from the viewpoint of handling properties during processing and physical properties of the composition. By constituting the diblock copolymer represented by AB, it has a structural unit derived from a vinyl monomer having an acidic group in block A, a structural unit derived from a vinyl monomer having a tertiary amino group in block B, and a quaternary ammonium base. It is thought that the structural unit derived from the vinyl monomer is localized, and can effectively act with a coloring material, a solvent, and a binder resin (alkali-soluble resin).

The content rate of the block A is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and even more preferably 50% by mass or more in 100% by mass of the total block copolymer. And 85% by mass or less is preferable, more preferably 80% by mass or less, still more preferably 75% by mass or less, and still more preferably 65% by mass or less. The content rate of the B block is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and even more preferably 30% by mass or more in 100% by mass of the total block copolymer. And 65 mass% or less is preferable, more preferably 60 mass% or less, still more preferably 55 mass% or less, still more preferably 50 mass% or less, and even more preferably 45 mass% or less. By adjusting the content rates of the A block and the B block within the above range, it is possible to balance heat resistance and dispersion performance when used as a dispersant.

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

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

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

The molecular weight of the block copolymer (a) is measured by gel permeation chromatography (hereinafter referred to as "GPC"). The weight average molecular weight (Mw) of the block copolymer (a) is preferably 5000 or more, more preferably 6000 or more, still more preferably 7000 or more, preferably 15000 or less, more preferably 12000 or less, furthermore Preferably it is 10000 or less. If the weight average molecular weight is within the above range, the dispersing performance when used as a dispersant becomes more favorable.

The molecular weight distribution (PDI) of the block copolymer (a) is preferably 2.0 or less, more preferably 1.6 or less, and even more preferably 1.4 or less. In addition, in this invention, molecular weight distribution (PDI) is what is calculated|required by (weight average molecular weight (Mw) of a block copolymer)/(number average molecular weight (Mn) of a block copolymer). The smaller the PDI, the narrower the molecular weight distribution and the homogeneous molecular weight copolymer becomes, and when the value is 1.0, the width of the molecular weight distribution is narrowest. That is, the lower limit of PDI is 1.0. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.0, those having a small molecular weight or a large molecular weight will be included.

(Method for producing block copolymer)

As a method for producing the block copolymer, a method of first preparing an A block by polymerization of a vinyl monomer, and polymerizing a B block monomer into the A block; A method of first preparing block B and polymerizing a monomer of block A on block B; After separately preparing the A block and the B block, the method of coupling the A block and the B block; Block A is first prepared, and a monomer composition containing a vinyl monomer capable of forming a structural unit represented by formula (2) on block B is polymerized, and some of the structural units represented by formula (2) in the obtained polymer A method of quaternizing a tertiary amine structure; A monomer composition containing a vinyl monomer capable of forming a structural unit represented by formula (2) is polymerized, and a monomer of block A is polymerized in the polymer, and part of the structural unit represented by formula (2) in the obtained polymer A method of quaternizing the tertiary amine structure of; A block and a block having the structural unit represented by formula (2) were separately prepared, and after coupling these blocks, the tertiary amine structure of a part of the structural unit represented by formula (2) in the obtained polymer was 4 A method of rapid fire, etc. are mentioned.

The polymerization method is not particularly limited, but living radical polymerization is preferred. That is, it is preferable that the block copolymer is polymerized by living radical polymerization. In the conventional radical polymerization method, not only the initiation reaction and the growth reaction, but also the stop reaction and the chain transfer reaction cause deactivation of the growth end, which tends to become a mixture of polymers having various molecular weights and non-uniform composition. On the other hand, the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method, and it is difficult to cause a stop reaction or chain movement, and because it grows without deactivation of the growth end, precise control of the molecular weight distribution and uniformity It is preferable from the viewpoint of easy production of the polymer of the composition.

The living radical polymerization method includes a method of using a transition metal catalyst (ATRP method) due to a difference in the method of stabilizing the polymerization growth terminal; A method using a sulfur-based reversible chain transfer agent (RAFT method); There are methods, such as a method of using an organic tellurium compound (TERP method). Since the ATRP method uses an amine-based complex, there are cases where it cannot be used without protecting the acidic group of the vinyl monomer having an acidic group. In the RAFT method, when various types of monomers are used, it is difficult to obtain a low molecular weight distribution, and there may be problems such as sulfur odor and coloring. Among these methods, it is preferable to use the TERP method from the viewpoint of diversity of available monomers, control of molecular weight in the polymer region, uniform composition, or coloring.

The TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a polymerization initiator, and examples include International Publication No. 2004/14848, International Publication No. 2004/14962, and International Publication No. It is a method described in Publication No. 2004/072126 and International Publication No. 2004/096870.

As a specific polymerization method of the TERP method, the following (a) to (d) can be mentioned.

(a) A vinyl monomer is polymerized using an organic tellurium compound represented by the general formula (11).

(b) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (11) and an azo polymerization initiator.

(c) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (11) and an organic ditelluride compound represented by the general formula (12).

(d) The vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (11), an azo polymerization initiator, and an organic ditelluride compound represented by the general formula (12).

[In General Formula (11), R ¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.

In General Formula (12), R ¹ represents a C 1 to C 8 alkyl group, an aryl group, or an aromatic heterocyclic group.]

The group represented by R ¹ is an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms, and is specifically as follows.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, oxy A linear or branched alkyl group such as a tyl group, and a cyclic alkyl group such as a cyclohexyl group, etc. are mentioned. Preferably, it is a C1-C4 linear or branched chain alkyl group, More preferably, it is a methyl group or an ethyl group.

As an aryl group, a phenyl group, a naphthyl group, etc. are mentioned.

As an aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, etc. are mentioned.

The groups represented by R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is specifically as follows.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, oxy A linear or branched alkyl group such as a tyl group, and a cyclic alkyl group such as a cyclohexyl group, etc. are mentioned. Preferably, it is a C1-C4 linear or branched chain alkyl group, More preferably, it is a methyl group or an ethyl group.

The group represented by R ⁴ is an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group, and specifically Is as follows.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, oxy Linear or branched chain alkyl groups such as a yl group, and cyclic alkyl groups such as a cyclohexyl group, etc. are mentioned. Preferably, it is a C1-C4 linear or branched chain alkyl group, More preferably, it is a methyl group or an ethyl group.

As an aryl group, a phenyl group, a naphthyl group, etc. are mentioned. Preferably it is a phenyl group.

Examples of the substituted aryl group include a phenyl group having a substituent and a naphthyl group having a substituent. As the substituent of the aryl group having the above substituent, for example, a halogen atom, a hydroxy group, an alkoxy group, an amino group, a nitro group, a cyano group, a carbonyl-containing group represented by -COR ⁴¹¹ (R ⁴¹¹ is a C1-C8 An alkyl group, an aryl group, an alkoxy group having 1 to 8 carbon atoms or an aryloxy group), a sulfonyl group, a trifluoromethyl group, and the like. Moreover, it is preferable that 1 or 2 of these substituents are substituted.

As an aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, etc. are mentioned.

As the alkoxy group, a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom is preferable. For example, a methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert- Butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, etc. are mentioned.

Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.

Examples of the amide group include -CONR ⁴²¹ R ⁴²² (R ⁴²¹ and R ⁴²² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).

As the oxycarbonyl group, a group represented by -COOR ⁴³¹ (R ⁴³¹ is a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms) is preferable, for example, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, n- Butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, phenoxycarbonyl group, etc. are mentioned. As a preferable oxycarbonyl group, a methoxycarbonyl group and an ethoxycarbonyl group are mentioned.

As the allyl group, -CR ⁴⁴¹ R ⁴⁴² -CR ⁴⁴³ =CR ⁴⁴⁴ R ⁴⁴⁵ (R ⁴⁴¹ , R ⁴⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁴³ , R ⁴⁴⁴ , R ⁴⁴⁵ are each independently Examples thereof include a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and each substituent may be connected in a cyclic structure).

As a propargyl group, -CR ⁴⁵¹ R ⁴⁵² -C≡CR ⁴⁵³ (R ⁴⁵¹ and R ⁴⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴⁵³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, or Silyl group) etc. are mentioned.

The organic tellurium compound represented by the general formula (11) is specifically (methyltelanylmethyl)benzene, (methyltellanylmethyl)naphthalene, ethyl-2-methyl-2-methyltelanyl-propionate, ethyl -2-Methyl-2-n-butyltelanyl-propionate, (2-trimethylsiloxyethyl)-2-methyl-2-methyltelanyl-propionate, (2-hydroxyethyl)-2- Methyl-2-methyltellanyl-propionate or (3-trimethylsilylpropargyl)-2-methyl-2-methyltellanyl-propionate, etc., International Publication No. 2004/14848, International Publication No. 2004/ The whole organic tellurium compound described in 14962, International Publication No. 2004/072126, and International Publication No. 2004/096870 can be illustrated.

Specific examples of the organic ditelluride compound represented by the general formula (12) include dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, and dicyclopropylditelluride. , Di-n-butylditelluride, di-s-butylditelluride, di-t-butylditelluride, dicyclobutylditelluride, diphenylditelluride, bis-(p-methoxyphenyl) Ditelluride, bis-(p-aminophenyl)ditelluride, bis-(p-nitrophenyl)ditelluride, bis-(p-cyanophenyl)ditelluride, bis-(p-sulfonylphenyl) Ditelluride, dinaphthylditelluride, dipyridylditelluride, etc. can be illustrated.

The azo-based polymerization initiator can be used without particular limitation as long as it is an azo-based polymerization initiator used in ordinary radical polymerization. For example, 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis (2-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-acetoxy-1-phenylethane), 2,2'-azobis (2-methylbutylamide), 2, 2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)(V-70), 2,2'-azobis(2-methylamidinopropane) dihydrochloride, 2,2'-azo Bis[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-propylazoformamide, 2,2'-azobis (N-butyl-2-methylpropionamide), or 2,2'-azobis (N-cyclohexyl-2-methylpropionamide) etc. can be illustrated.

The polymerization process is carried out in a container substituted with an inert gas, to the vinyl monomer and the organic tellurium compound of the general formula (11), for the purpose of accelerating the reaction, controlling the molecular weight and molecular weight distribution, etc. depending on the type of the vinyl monomer. The crude polymerization initiator and/or the organic ditelluride compound of the general formula (12) are mixed. At this time, nitrogen, argon, helium, etc. are mentioned as an inert gas. Preferably, argon and nitrogen are good.

The amount of vinyl monomer used in the above (a), (b), (c) and (d) may be appropriately adjusted according to the properties of the target copolymer. It is preferable to set the vinyl monomer to 5 mol to 10000 mol per 1 mol of the organic tellurium compound of the general formula (11).

When the organic tellurium compound of the general formula (11) and an azo polymerization initiator of the above (b) are used in combination, the azo polymerization initiator is 0.01 mol to 10 mol with respect to 1 mol of the organic tellurium compound of the general formula (11). desirable.

When the organic tellurium compound of the general formula (11) of the above (c) and the organic ditelluride compound of the general formula (12) are used in combination, the general formula (12) per 1 mol of the organic tellurium compound of the general formula (11) It is preferable to set the organic ditelluride compound of 0.01 mol to 100 mol.

When the organic tellurium compound of the general formula (11) of the above (d), the organic ditelluride compound of the general formula (12), and an azo polymerization initiator are used in combination, per 1 mol of the organic tellurium compound of the general formula (11) It is preferable that the organic ditelluride compound of the general formula (12) is 0.01 mol to 100 mol, and the azo polymerization initiator is preferably 0.01 mol to 100 mol with respect to 1 mol of the organic tellurium compound of the general formula (11).

The polymerization reaction can be carried out even without a solvent, but the mixture may be stirred using a non-protic solvent or a protic solvent generally used in radical polymerization. Aprotic solvents that can be used include, for example, anisole, benzene, toluene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methylethylketone), Dioxane, propylene glycol monomethyl ether acetate, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate, trifluoromethylbenzene, and the like can be exemplified. In addition, as a protic solvent, for example, water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol or diacetone alcohol Etc. can be illustrated.

The amount of the solvent used may be appropriately adjusted, for example, 0.01 ml or more is preferable, more preferably 0.05 ml or more, still more preferably 0.1 ml or more, and 50 ml or less is preferable, for example, per 1 g of vinyl monomer, It is more preferably 10 ml or less, and still more preferably 1 ml or less.

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

After completion of the polymerization reaction, the target copolymer can be separated from the obtained reaction mixture by removing the solvent to be used and the remaining vinyl monomer by a conventional separation and purification means.

The block copolymer of the present invention can be obtained by sequentially polymerizing a vinyl monomer constituting a block by, for example, living radical polymerization. Specifically, in the case of the AB block, the vinyl monomer constituting the A block is polymerized by a living radical polymerization method, and the A block is polymerized, and after the A block is polymerized, the vinyl monomer constituting the B block is polymerized. , A polymerization method including a step of polymerizing a B block; In the case of the ABA block, a vinyl monomer constituting one of the two A blocks is polymerized by a living radical polymerization method to polymerize one A block, and after polymerizing one A block, a B block is formed. The steps of polymerizing the vinyl monomer to be polymerized to polymerize the block B, and the step of polymerizing the vinyl monomer constituting the other block of the two A blocks after polymerizing the B block and polymerizing the other block A. The polymerization method to be provided, etc. are mentioned.

The growth end of the copolymer obtained by the polymerization reaction is in the form of -TeR ¹ derived from a tellurium compound (wherein R ¹ is the same as above), and is deactivated by operation in air after the polymerization reaction is completed. There are cases where atoms remain. Since the copolymer in which the tellurium atom remains at the terminal is colored or the thermal stability is inferior, it is preferable to remove the tellurium atom.

Examples of the method for removing the tellurium atom include a radical reduction method using tributylstannan or a thiol compound; A method of adsorbing with activated carbon, silica gel, activated alumina, activated clay, molecular sieve, and polymer adsorbent; A method of adsorbing metal with an ion exchange resin or the like; A liquid-liquid that oxidizes and decomposes the tellurium atom at the end of the copolymer by adding a peroxide such as hydrogen peroxide or benzoyl peroxide, or blowing air or oxygen into the system, and removing residual tellurium compounds by washing with water or combining an appropriate solvent. Extraction or solid-liquid extraction; A purification method in a solution state, such as limit filtration in which only a specific molecular weight or less is extracted and removed, can be used, or a combination of these methods can also be used.

In the case of quaternizing the tertiary amine group of the structural unit represented by formula (2), examples of the quaternizing agent include halogenated alkyl such as methyl chloride, ethyl chloride, methyl bromide, and methyl iodide; Halogenated aralkyls such as benzyl chloride, benzyl bromide, and benzyl iodide; Diaryl sulfate such as diphenyl sulfate; Dimethyl sulfate; Dialkyl sulfates such as diethyl sulfate and di-n-propyl sulfate; and aromatic sulfonic acid alkyls such as methyl p-toluenesulfonic acid and ethyl p-toluenesulfonic acid. Among these, preferably, aralkyl halogenated such as benzyl chloride, benzyl bromide, and benzyl iodide, dialkyl sulfates such as dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate, methyl p-toluenesulfonic acid, ethyl p-toluenesulfonic acid And aromatic sulfonic acid alkyl, more preferably benzyl chloride, dimethyl sulfate, and methyl p-toluenesulfonic acid. In the structure after quaternization, an alkyl group and an aralkyl group derived from a quaternizing agent are introduced. Therefore, by measuring the amount of the alkyl group and the aralkyl group introduced by quaternization, the amount of the structural unit represented by the formula (1) can be estimated.

As a method of quaternizing the tertiary amine structure of a part of the structural unit represented by formula (2) in the polymer, a method of bringing the polymer and a quaternizing agent into contact is exemplified. Specifically, after polymerization of a monomer composition containing a vinyl monomer capable of forming a structural unit represented by formula (2), a method of adding a quaternizing agent to the reaction solution and stirring is exemplified. The temperature of the reaction solution to which the quaternizing agent is added is preferably 25°C to 65°C, more preferably 55°C to 65°C, the stirring time is preferably 1 to 40 hours, more preferably 5 hours to It's 20 hours. When adding a quaternizing agent, it is also preferable to dilute the reaction solution after polymerization. Examples of the solvent added for dilution include a solvent that can be used in the polymerization reaction, a protic solvent, and a mixed solvent of a solvent used in the polymerization reaction and a protic solvent, and appropriately selected according to the solubility of the target block copolymer. Just do it. Methanol is more preferable as the protic solvent.

(b) aromatic compounds

The dispersant composition of the present invention contains at least one aromatic compound selected from the group consisting of (b) an aromatic dicarboxylic acid imide, an acidic group-containing aromatic compound, and a phenolic hydroxy group-containing aromatic compound. When the dispersant composition contains (b) an aromatic compound, the dispersibility becomes good. (b) Only one type of aromatic compound may be mixed, and two or more types may be used in combination.

The aromatic dicarboxylic acid imide has an aromatic ring and an imide group (-C(=O)NHC(=O)-) directly bonded to the aromatic ring in a molecule. The imide group may have both ends bonded to one aromatic ring, or may be bonded to each different aromatic ring, but it is preferable that both ends are bonded to one aromatic ring. As the aromatic dicarboxylic acid imide, a compound represented by General Formula (3) is preferable.

[In General Formula (3), ring A represents an aromatic ring which may have a substituent.]

In General Formula (3), the aromatic ring constituting ring A is a ring structure having aromaticity. As said aromatic ring, both a monocyclic ring and a condensed ring are contained. As the monocyclic ring, a 5 or 6 membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable. As the condensed ring, a 2-5 condensed ring is preferable, and a naphthalene ring, an anthracene ring, a phenanthrene ring, and an indole ring are preferable. Among these, as a ring structure, it is preferable not to contain a hetero atom as an atom constituting the ring structure. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.

The following compounds are mentioned as a concrete example of the said aromatic dicarboxylic acid imide.

The acidic group-containing aromatic compound has an aromatic ring and an acidic group directly bonded to the aromatic ring in a molecule. Examples of the acidic group include a carboxyl group (-COOH), a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-OPO ₃ H ₂ ), a phosphonic acid group (-PO ₃ H ₂ ), and a phosphinic acid group (-PO ₂ H ₂ ). Can be mentioned. The number of acidic groups may be one or may have a plurality of them. Moreover, when it has multiple acidic groups, you may have multiple types of acidic groups. As the acidic group-containing aromatic compound, a compound represented by the general formula (4) (ie, aromatic carboxylic acid, aromatic sulfonic acid, aromatic phosphonic acid) is preferable.

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

In General Formula (4), the aromatic ring constituting ring A is a ring structure having aromaticity. As said aromatic ring, both a monocyclic ring and a condensed ring are contained. As the monocyclic ring, a 5 or 6 membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable. As the condensed ring, a 2-5 condensed ring is preferable, and a naphthalene ring, an anthracene ring, a phenanthrene ring, and an indole ring are preferable. Among these, as a ring structure, it is preferable not to contain a hetero atom as an atom constituting the ring structure. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.

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

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

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

The phenolic hydroxy group-containing aromatic compound has an aromatic ring in a molecule and a hydroxy group directly bonded to the aromatic ring. The number of hydroxyl groups may be one or may have a plurality of them. As the phenolic hydroxy group-containing aromatic compound, a compound represented by General Formula (5) is preferable.

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

In General Formula (5), the aromatic ring constituting ring A is a ring structure having aromaticity. As said aromatic ring, both a monocyclic ring and a condensed ring are contained. As the monocyclic ring, a 5 or 6 membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable. As the condensed ring, a 2-5 condensed ring is preferable, and a naphthalene ring, an anthracene ring, a phenanthrene ring, an indole ring, a coumarin ring, and a xanthene ring are suitable. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.

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

(c) tertiary amine compound

The dispersant composition contains (c) a tertiary amine compound. The (c) tertiary amine compound has a tertiary amine structure in its molecule. When the dispersant composition contains (c) a tertiary amine compound, salt formation with the (b) aromatic compound becomes possible. (c) Tertiary amine compounds may be used alone or in combination of two or more.

As said (c) tertiary amine compound, a compound represented by general formula (6) or a compound represented by general formula (7) is preferable, and a compound represented by general formula (7) is more preferable. By blending the compound represented by the general formula (7) as the (c) tertiary amine compound, the luminance of the coating film formed from the coloring composition is improved.

[In 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. Further, R ⁶² and R ⁶³ may be bonded to each other to form a cyclic structure.]

Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R ⁶¹ , R ⁶² and R ⁶³ include a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an arral having 7 to 10 carbon atoms. A kill group and a C7-10 alkylaryl group are mentioned.

As a compound represented by the general formula (6), trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N- Aliphatic amines such as ethyl diamylamine; Aromatic amines such as N,N-dimethylaniline and N,N-diethylaniline; Alicyclic amines, such as N,N-dimethyl-cyclohexylamine, and N,N-diethyl-cyclohexylamine, etc. are mentioned.

[In the general formula (7), R ⁷¹ represents a C 2 to C 6 divalent hydrocarbon group which may have a substituent, and R ⁷² and R ⁷³ are each independently a hydrogen atom or a C 1 to C which may have a substituent It represents 10 hydrocarbon groups. Further, R ⁷² and R ⁷³ may be bonded to each other to form a cyclic structure.]

Examples of the divalent C2-C6 hydrocarbon group represented by R ⁷¹ include a C2-C6 alkylene group. Examples of the substituents of the divalent C2-C6 hydrocarbon group represented by R ⁷¹ include a C1-C10 chain alkyl group, a C1-C10 cyclic alkyl group, a C6-C10 aryl group, and a C7-10 aralkyl group. And an alkylaryl group having 7 to 10 carbon atoms.

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

As the compound represented by the general formula (7), a cyclic amidine compound represented by the general formula (8) is preferable.

[In General Formula (8), R ⁸⁰ to R ⁸⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. n is an integer of 1-4. m is an integer of 1-4.]

The following compounds are mentioned as a concrete example of the compound represented by said general formula (8).

It is preferable that the said dispersant composition contains a solvent. As the solvent, an organic solvent can be used, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monoethyl ether, dipropylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether ; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether Acetate, methoxybutyl 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 mono Glycol alkyl ether acetates such as methyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl Ketones such as ketone, methylnonyl ketone, and methoxymethylpentanone; 1 such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, methoxymethylpentanol, glycerin, benzyl alcohol, etc. Polyhydric or polyhydric alcohols; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl; Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Amylformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethylbenzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxy Chain or cyclic esters such as butyl oxypropionate and γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; And nitriles such as acetonitrile and benzonitrile. The organic solvent contained in the dispersant composition may be one type or a plurality of types.

The dispersant composition can be adjusted by mixing (a) a block copolymer, (b) an aromatic compound, (c) a tertiary amine compound, and a solvent as necessary. In addition, after mixing, (b) aromatic compound and (c) tertiary amine compound reacted to form an organic salt, so that (b) aromatic compound and (c) tertiary amine compound are mixed in advance. One mixture (for example, (d) a salt consisting of an aromatic compound and a tertiary amine compound) and (a) a block copolymer may be mixed and prepared. Mixing of each raw material can be performed using a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, and a kneader, for example. The mixing temperature when preparing the dispersant composition is preferably 50° C. or higher, more preferably 55° C. or higher, still more preferably 60° C. or higher, preferably 75° C. or lower, and more preferably 70° C. or lower, More preferably, it is 65 degrees C or less.

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

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

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

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

When the sum of the (a) block copolymer, (b) aromatic compound and (c) tertiary amine compound is 100 parts by mass, the amount of the solvent is preferably 50 parts by mass or more, and more preferably 100 parts by mass. It is at least 200 parts by mass, more preferably at least 200 parts by mass, preferably at most 500 parts by mass, more preferably at most 300 parts by mass, and still more preferably at most 250 parts by mass.

The acid value of the solid content of the dispersant composition is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g or more, 70 mgKOH/g or less is preferable, and more preferably 65 mgKOH/ g or less, more preferably 60 mgKOH/g or less. If the acid value is 5 mgKOH/g or more, the solubility in alkali is high and the rate of dissolution in alkali is faster, and if it is 70 mgKOH/g or less, the viscosity of the coloring composition does not become too high, and the resist composition has more coating properties. It becomes good. Here, the solid content is a component other than a solvent.

The amine value of the solid content of the dispersant composition is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, still more preferably 50 mgKOH/g or more, 150 mgKOH/g or less is preferable, and more preferably 120 mgKOH/ g or less, more preferably 95 mgKOH/g or less. When the amine value is 10 mgKOH/g or more, the aging stability of the viscosity of the colored composition is more improved, and when it is 150 mgKOH/g or less, an increase in the viscosity of the colored composition can be suppressed.

(Coloring composition)

The coloring composition of the present invention contains the dispersant composition, a coloring material, a dispersion medium, and a binder resin.

(Coloring material)

The kind of the coloring material may be appropriately selected according to the application, and examples thereof include pigments and dyes. It is preferable that the said coloring composition contains a pigment as a coloring material from a viewpoint of light resistance and heat resistance. Although any of an organic pigment and an inorganic pigment may be sufficient as a pigment, an organic pigment containing an organic compound as a main component is especially preferable. As a pigment, each color pigment, such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, and a purple pigment, is mentioned, for example. The structure of the pigment is azo pigments such as monoazo pigments, diazo pigments, condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments And polycyclic pigments such as pigments, indigo pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments and perinone pigments. The number of pigments contained in the coloring composition may be only one type, or may be plural types for adjustment such as chromaticity.

As a specific example of a pigment, 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, Red pigments such as 177, 178, 179, 187, 200, 202, 208, 210, 215, 224, 242, 254, 255, 264, 269; 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, Yellow pigments such as 150, 151, 154, 155, 166, 167, 168, 170, 180, 185, 188, 193, 194, 213; C.I. Orange pigments such as Pigment Orange 36, 38, 43; C.I. Blue pigments, such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 22, 60; C.I. Pigment Green 7, 36, 58, 59, 62, 63, aluminum phthalocyanine, polyhalogenated aluminum phthalocyanine, aluminum phthalocyanine hydroxide, diphenoxyphosfinyloxyaluminum phthalocyanine, diphenylphosphinyloxy aluminum phthalocyanine, polyhalogenated diphenoxyphosphi Green pigments such as niloxy aluminum phthalocyanine and polyhalogenated diphenylphosphinyloxy aluminum phthalocyanine; C.I. Purple pigments, such as Pigment Violet 23, 32, 50, etc. are mentioned. Among these pigments, 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 and the like are preferred.

In the present invention, the dispersant composition is preferably used with a coloring material containing a phthalocyanine pigment, specifically 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, CI 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, polyhalogenated aluminum phthalocyanine, aluminum phthalocyanine hydrooxide, diphenoxyphosfinyloxy aluminum phthalocyanine, diphenylphosphinyloxy aluminum phthalocyanine, polyhalogenated diphenoxyphosfinyloxy aluminum phthalocyanine, polyhalogenated diphenylphosphine It is preferably used together with a coloring material containing finyloxy aluminum phthalocyanine or the like. More preferably, it is good to use it with a coloring material containing a polyhalogenated phthalocyanine-based 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 the red pigment, the green pigment, and the blue pigment may be mixed and used. Examples of the black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoint of the light-shielding rate and image characteristics.

The number average particle diameter of the coloring material may be appropriately selected depending on the application, and there is no particular limitation. From the viewpoint of high transparency and high contrast, the colored composition preferably contains a coloring material having a number average particle diameter of 10 nm to 150 nm.

The coloring material may contain a dye derivative as a dispersing aid. As the dye derivative, it is preferable to contain an acidic dye derivative having an acidic group for adsorbing by ion bonding with a tertiary amino group or a quaternary ammonium base group in the resin type dispersant. This dye derivative has an acidic functional group introduced into the dye skeleton. As the dye skeleton, a skeleton identical or similar to the coloring material constituting the coloring composition, and the skeleton identical or similar to the compound used as a raw material for the coloring material is preferable. 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, and a perylene dye skeleton. As the acidic group introduced into the dye skeleton, a carboxyl group, a phosphoric acid group, and a sulfonic acid group are preferable. Further, for convenience of synthesis and from the strength of acidity, a sulfonic acid group is preferred. Moreover, although the acidic group may be directly bonded to the dye skeleton, hydrocarbon groups such as an alkyl group and an aryl group; You may bond to the dye skeleton through an ester, ether, sulfonamide, or urethane bond. Although there is no particular limitation on the amount of the dye derivative used, it is preferably 4 parts by mass to 17 parts by mass per 100 parts by mass of the coloring material.

The upper limit of the content of the coloring material in the coloring composition is usually 80% by mass, preferably 75% by mass, and more preferably 70% by mass in the total solid content of the coloring composition from the viewpoint of luminance. Moreover, the lower limit of the content of the coloring material 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 is a component other than the dispersion medium described later.

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

(Dispersion medium)

As the dispersion medium, the colored composition can be appropriately selected and used as long as it disperses or dissolves other components constituting the colored composition, does not react with these components, and has appropriate volatility. For example, conventionally known organic solvents can be used, and those exemplified as solvents for the dispersant composition can be used. The organic solvent is preferably glycol alkyl ether acetates, monohydric or polyhydric alcohols from the viewpoints of dispersibility such as a coloring material, solubility of a dispersant, and coating properties of a colored composition. The number of solvents contained in the coloring composition may be one or more than one.

In the case of forming pixels of a color filter by photolithography, the boiling point of the dispersion medium is preferably 100°C to 200°C (under pressure 1013.25 hPa conditions. Hereinafter, the boiling points are all the same), and more preferably 120°C to 170°C. desirable. Among the above dispersion media, glycol alkyl ether acetates are preferred from the viewpoint of a good balance of coating properties and surface tension, and relatively high solubility of constituents in the colored composition. Glycol alkyl ether acetates may be used alone or in combination with other dispersion media. In this case, it is also preferable to use a dispersion medium having a boiling point of 150°C or higher. By using such a high-boiling dispersion medium in combination, the colored composition becomes difficult to dry, and breakage of the mutual relationship of the colored composition due to rapid drying can be suppressed. 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 with respect to 100% by mass of the entire dispersion medium. When the content ratio is 3% by mass or more, it is possible to suppress the occurrence of foreign matter defects due to precipitation and solidification of a coloring material or the like at the tip of the slit nozzle. If it is 50 mass% or less, the drying speed of a colored composition becomes slow, and in manufacturing a color filter mentioned later, prolonged drying time and occurrence of problems, such as a pin trace of prebaking, can be suppressed. Further, the dispersion medium having a boiling point of 150°C or higher may be glycol alkyl ether acetates, and in this case, a dispersion medium having a boiling point of 150°C or higher may not be separately contained.

In the case of forming pixels of a color filter 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. By setting the boiling point to 130° C. or higher, the uniformity of the resulting coating film becomes good. Moreover, by setting the boiling point to 300°C or less, residual solvent in the coating film after thermal calcination can be reduced, and problems in quality and prolonged drying time can be suppressed. In addition, the vapor pressure of the dispersion medium may be usually 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less from the viewpoint of uniformity of the resulting coating film.

In addition, in the manufacture of color filters by the inkjet method, since the ink emitted from the nozzle is very fine, ranging from several pL to several tens of pL, the dispersion medium evaporates and the ink is concentrated and dried before landing around the nozzle opening or in the pixel bank. There is a tendency. In order to avoid this, it is preferable that the boiling point of the dispersion medium is high, and specifically, it is preferable to include a dispersion medium having a boiling point of 180°C or higher. More preferably, it contains a dispersion medium having a boiling point of 200°C or higher, particularly preferably 220°C or higher. In addition, the high boiling point solvent having a boiling point of 180°C or higher is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more with respect to 100% by mass of the total dispersion medium contained in the colored composition. . By setting it as more than the said lower limit, there exists a tendency for the effect of preventing evaporation of a solvent from droplets to fully exhibit.

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

(Binder resin)

The colored composition of the present invention contains a binder resin (however, the block copolymer (a) is excluded). Thereby, alkali developability of a colored composition and binding property to a board|substrate can be improved. Although it does not specifically limit as such a binder resin, It is preferable that it is a resin which has acidic groups, such as a carboxyl group and a phenolic hydroxy group. As the binder resin, for example, to a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, a resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy groups of the copolymer, or Alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxy group generated by the addition reaction; A linear alkali-soluble resin containing a carboxyl group in the main chain; Resin in which an epoxy group-containing unsaturated compound was added to the carboxy group portion of the carboxy group-containing resin; (Meth)acrylic resin; And epoxy (meth)acrylate resins having a carboxyl group, and these may be used alone or in combination of two or more.

Examples of the binder resin include a random copolymer containing a structural unit derived from a carboxyl group-containing vinyl monomer and a structural unit derived from (meth)acrylate and styrene, a synthetic resin in which a (meth)acrylic group is introduced into an epoxy resin, and a carboxyl group-containing vinyl. A random copolymer containing a structural unit derived from a monomer and a structural unit derived from a (meth)acrylate is preferable. As the carboxy group-containing vinyl monomer, (meth)acrylic acid is preferable. As the (meth)acrylate, 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-hydroxylethyl (meth) acrylate, 4 -Hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycerol mono (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, And tetrahydrofurfuryl (meth)acrylate.

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

Among these, it is preferable that it is a random copolymer of a carboxy group-containing vinyl monomer and (meth)acrylate. Specific examples of such a copolymer include a random copolymer of (meth)acrylic acid and butyl (meth)acrylate, a random copolymer of (meth)acrylic acid and benzyl (meth)acrylate, and (meth)acrylic acid and butyl (meth)acrylate. And a random copolymer of benzyl (meth)acrylate and the like. 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 a copolymer of a carboxyl group-containing vinyl monomer and (meth)acrylate, the content of (meth)acrylic acid is usually 5% by mass to 90% by mass, preferably 10% by mass to 70% by mass, among all monomer components. It is more preferable that it is 20 mass%-70 mass %.

The binder resin may have a carbon-carbon double bond capable of radical polymerization in the side chain. By having a double bond in the side chain, since the photocurability of the colored composition according to the present invention is increased, resolution and adhesion can be further improved. As a method of introducing a radically polymerizable carbon-carbon double bond into the side chain, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o- (or m-, Alternatively, a method of reacting a compound such as p-) vinylbenzyl glycidyl ether with the acidic group of the binder resin is exemplified.

It is preferable that it is 3,000-100,000, as for Mw of a binder resin, it is more preferable that it is 5,000-50,000, and it is still more preferable that it is 5,000-20,000. When Mw of the binder resin is 3,000 or more, the heat resistance, film strength, etc. of the colored layer formed of the colored composition become good, and when Mw is 100,000 or less, the alkali developability of this coating film is further improved.

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

The number of binder resins contained in the coloring composition may be one type or a plurality of types. In the coloring composition, the content of the binder resin is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass, and 20 parts by mass to 80 parts by mass per 100 parts by mass of the coloring material. More preferable.

(Crosslinking agent)

The colored composition may contain a crosslinking agent. The crosslinking agent refers to a compound having two or more polymerizable groups. As a polymerizable group, an ethylenic unsaturated group, an oxiranyl group, an oxetanyl group, an N-alkoxymethylamino group, etc. are mentioned, for example. As the crosslinking agent, a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable. The crosslinking agent may be used alone or in combination of two or more.

Specific examples of the compound having two or more (meth)acryloyl groups include polyfunctional (meth)acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, and caprolactone-modified polyfunctional (meth)acrylate , Alkylene oxide-modified polyfunctional (meth)acrylate, polyfunctional urethane (meth)acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, (meth)acrylate having a hydroxyl group and an acid anhydride The polyfunctional (meth)acrylate etc. which have a carboxy group obtained by reacting are mentioned.

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; And trivalent or higher aliphatic polyhydroxy compounds such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of the (meth)acrylate having a hydroxy group include 2-hydroxyethyl (meth)acrylate, trimethylolpropanedi (meth)acrylate, pentaerythritol tri (meth)acrylate, dipentaerythritol penta ( Meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerol di(meth)acrylate, etc. are mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; And tetrabasic acid dianhydrides such as pyromellitic anhydride, biphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride.

In the colored composition of the present invention, the content of the crosslinking agent is preferably 10 parts by mass to 1,000 parts by mass, and particularly preferably 20 parts by mass to 500 parts by mass with respect to 100 parts by mass of the coloring material. If the content of the crosslinking agent is too small, there is a fear that sufficient curability may not be obtained. On the other hand, when the amount of the crosslinking agent is too large, the alkali developability is lowered in the colored composition of the present invention, and grease, film residues, etc. tend to occur easily on the substrate or the light-shielding layer of the unexposed portion.

(Photopolymerization initiator)

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

Examples of the photopolymerization initiator include thioxanthone compounds, acetphenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone compound, a polynuclear quinone compound, a diazo compound, an imide sulfonate compound, etc. are mentioned. Photoinitiators 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 parts by mass to 120 parts by mass, and particularly preferably 1 part by mass to 100 parts by mass, based on 100 parts by mass of the crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, there is a risk that curing may be insufficient due to exposure, whereas if it is too large, the formed colored layer tends to be easily detached from the substrate during development.

(Other formulations)

In addition to the above compounding agent, other compounding agents may be added to the colored composition as long as the range does not impair the preferred physical properties of the present 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, and phenolic antioxidants. Other antioxidants, ultraviolet absorbers, light stabilizers, preservatives, mold inhibitors, anti-aggregation agents, adhesion improvers, development improvers, storage stabilizers, and the like may be mentioned.

As a sensitizing dye, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3 '-Diaminobenzophenone, 3,4-diaminobenzophenone, 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylamino Phenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl) 1,3,4- Oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethyl Aminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, ( p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, and the like.

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

As a nonionic surfactant, a fluorine-based surfactant (1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluoro Octylhexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene Glycoldi (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc.), silicone surfactant, polyoxy Ethylene surfactants (polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, poly Oxyethylene glycerin fatty acid esters, pentaerythritic fatty acid esters, polyoxyethylene pentaerythritic fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxyethylene sorbit Fatty acid esters, etc.), etc. are mentioned.

As anionic surfactants, alkyl sulfonates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfuric acid ester salts, higher alcohol sulfuric acid ester salts, aliphatic alcohol sulfuric acid ester salts, poly Oxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphoric acid ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, and special high molecular surfactants.

Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.

Examples of amphoteric surfactants include betaine compounds, imidazolium salts, imidazolines, amino acids, and the like.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin.

As organic carboxylic acid compounds, monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, tricarvalyl acid, aconitic acid, benzoic acid, phthalic acid, etc. And carboxylic acids to which a carboxyl group is bonded through a carbon bond.

Examples of the organic carboxylic anhydride include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutal anhydride, 1,2-cyclo anhydride Hexene dicarboxylic acid, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride, and the like.

<Production method of colored composition and color filter>

The coloring composition can be prepared by mixing a dispersant composition, a coloring material, a dispersion medium, a binder resin, a crosslinking agent, a photopolymerization initiator, and other additives, if necessary. Further, the colored composition may be prepared by mixing (a) a block copolymer, (b) an aromatic compound, (c) a tertiary amine compound, a coloring material, a dispersion medium, a binder resin, and other components as necessary. Mixing can be performed using a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, and a kneader. It is preferable to filter the coloring composition after mixing. Examples of other additives include a pH adjuster, an antioxidant, an ultraviolet absorber, a light stabilizer, an antiseptic agent, an anti-mold agent, a surfactant, an anti-aggregation agent, and the like.

Since the said colored composition has alkali developability, it can be used suitably as a color filter use.

The color filter of the present invention is provided with a colored layer formed using the colored composition. As a method of manufacturing a color filter, the following method is mentioned, for example. First, thermoplastic resin sheets such as polyester resin, polyolefin resin, polycarbonate resin, polymethyl methacrylate resin, epoxy resin, unsaturated polyester resin, thermosetting resin sheet such as poly(meth)acrylic resin, various glasses, etc. On the transparent substrate of, for example, after applying the colored composition of the present invention in which a red pigment is dispersed, prebaking is performed to evaporate a solvent (dispersion medium) to form a coating film. Then, after exposure to the coating film through a photomask, it is developed using an alkali developer (such as an organic solvent or an aqueous solution containing a surfactant and an alkaline compound) to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed. Then, using each green or blue colored composition, in the same manner as described above, coating, pre-baking, exposure, development and post-baking of each colored composition were performed, and the green pixel array and the blue pixel array were placed on the same substrate. It is formed sequentially on the phase. Thereby, a color filter in which pixel arrays of three primary colors of red, green and blue are disposed on a substrate is obtained. However, in the present invention, the order of forming each color pixel is not limited to the above.

When applying the colored composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method, and a bar coating method can be employed. In particular, a spin coating method, It is preferable to employ a slit die coating method.

On the pixel pattern thus obtained, after forming a protective film as necessary, a transparent conductive film (such as ITO) is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to form a color filter. Further, a black matrix may be formed on a transparent substrate used for forming a pixel array of three primary colors of red, green and blue.

The color filter of the present invention has high dimensional accuracy and the like, and can be suitably used for a color liquid crystal display element, a color imaging tube element, a color sensor, an organic EL display element, electronic paper, or the like.

In addition, the colored composition is suitable as a colored column spacer supporting a TFT substrate and a color filter substrate positioned between a liquid crystal layer and a color filter substrate, since the above-described colored composition has a low viscosity and excellent luminance of a coating film (colorant) formed of the colored composition. Can be used. For example, the composition of high optical density (Optical Depth: OD) described in Japanese Unexamined-Japanese-Patent No. 2015-191234 is mentioned.

(Example)

Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited at all to the following examples, and it is possible to implement it with appropriate changes within a range that does not change the subject matter. In addition, the polymerization rate of the dispersant and the binder resin, the weight average molecular weight (Mw), the molecular weight distribution (PDI), the amine value and the acid value, and the viscosity and brightness of the colored composition were evaluated according to the following method.

In addition, the meaning of the abbreviation is as follows.

BTEE: ethyl-2-methyl-2-n-butyltelanyl-propionate

DBDT: dibutylditelluride

AIBN: 2,2'-azobis (isobutyronitrile)

MMA: methyl methacrylate

BMA: butyl methacrylate

EHMA: 2-ethylhexyl methacrylate

BzMA: Benzyl methacrylate

M4EGM: Methoxy polyethylene glycol monomethacrylate (brand 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: Phthalimide Diazabicycloundecene

PMA: propylene glycol monomethyl ether acetate

MP: 1-methoxy-2-propanol

(Polymerization rate)

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

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))

It was determined by gel permeation chromatography (GPC) using a high-performance liquid chromatography (manufactured by Tosoh Corporation, format: HLC8320). One column was SHODEX KF-603 (Φ 6.0 mm × 150 mm) (manufactured by SHODEX), 30 mmol/L lithium bromide-30 mmol/L acetic acid-N-methylpyrrolidone as a mobile phase, and a differential refractive index detector as a detector. . Measurement conditions were a column temperature of 40°C, a sample concentration of 20 mg/mL, a sample injection amount of 10 μL, and a flow rate of 0.2 mL/min. A calibration curve (calibration curve) was prepared using polystyrene (molecular weight 427,000, 190,000, 96,400, 37,400, 10,200, 2,630, 906) as a standard substance, and the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured. The molecular weight distribution (PDI = Mw/Mn) was calculated from these measured values.

(Amine number)

The amine value is expressed by the mass of the basic component and the equivalent of potassium hydroxide (KOH) per 1 g of solid content. The measurement sample was dissolved in tetrahydrofuran, and the obtained solution was subjected to neutralization titration with a 0.1 mol/L hydrochloric acid/2-propanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). The inflection point of the appropriate pH curve was used as the appropriate end point, and the amine value (B) was calculated by the difference equation.

B=56.11×Vs×0.1×f/w

B: Amine number (mgKOH/g)

Vs: Amount of 0.1 mol/L hydrochloric acid/2-propanol solution required for titration (mL)

f: titer of 0.1 mol/L hydrochloric acid/2-propanol solution

w: Mass of the measurement sample (g) (converted solid content)

(Acid value)

The acid value represents the mass of potassium hydroxide required to neutralize the acidic component per gram of solid content. The measurement sample was dissolved in tetrahydrofuran, a few drops of a phenolphthalein ethanol solution was added as an indicator, and neutralization titration was performed with a 0.1 mol/L potassium hydroxide/ethanol solution. The acid value (A) was calculated by the following equation.

A=56.11×Vs×0.1×f/w

A: acid value (mgKOH/g)

Vs: Amount of 0.1 mol/L potassium hydroxide/ethanol solution required for titration (mL)

f: titer of 0.1 mol/L potassium hydroxide/ethanol solution

w: Mass of the measurement sample (g) (converted solid content)

(Viscosity)

Using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.), viscosity was measured at a rotor rotation speed of 60 rpm at 25°C using a controller rotor (1° 34'×R24).

After preparation, the colored composition was stored at 25° C. for 2 hours, and then the viscosity was measured. A viscosity of less than 10 mPa·s was evaluated as "A", and a viscosity of 10 mPa·s or more was evaluated as "B".

(Luminance)

A colored composition was applied to a glass plate, and after drying, a coating film was formed by heat treatment at 230° C. for 30 minutes to produce a colored glass. The colored glass plate was set in a spectrophotometer (trade name: CM-3700d, manufactured by Konica Minolta Sensing Co., Ltd.), and the transmittance of the C light source in the XYZ coordinate axis was measured. The Y value at this time was adopted as the luminance (Y). In Table 2, the luminance is colored composition No. 1-8 are colored composition No. It evaluated based on the luminance of the colored glass plate using 8 as a reference, and the difference (measured value-reference value) between the measured value and the reference value was 0.4 or more as "A", the difference exceeding 0 and less than 0.4 as "B", and the difference as 0 as "C". . In addition, coloring composition No. 9-11 are coloring composition No. It evaluated based on the luminance of the colored glass plate using 11, and the difference (measured value-reference value) of the measured value and the reference value was more than 0 and less than 0.2 as "A", and the difference was 0 as "B".

<Production of block copolymer>

In a flask equipped with an argon gas inlet tube and a stirrer, 46.1g of MMA, 22.2g of BMA, 20.9g of EHMA, 8.1g of BzMA, 8.1g of M4EGM, 8.1g of MAA, 0.82g of AIBN, 80.5g of PMA were added.After argon substitution, BTEE 7.49 g and 4.61 g of DBDT were added and reacted at 60°C for 15 hours to polymerize the A block. The polymerization rate was 99%.

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

After completion of the reaction, the reaction solution was diluted by adding methanol (165 g) substituted with argon in advance, and 15.3 g of BzCl was added to the diluted solution, followed by reacting at 60° C. for 10 hours to quaternize.

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

<Preparation of dispersant composition>

(Dispersant composition No. A)

To a flask equipped with a stirrer, 87.5 g of a block copolymer, 8.91 g of PI, 9.23 g of DBU, 110 g of PMA, and 110 g of MP were added, followed by heating and mixing at 60°C for 20 hours to prepare a dispersant composition.

(Dispersant composition No. B to H)

The formulation of each component was changed as shown in Table 1, and the dispersant composition No. In the same manner as in the preparation method of A, dispersant composition No. I got B~H.

<Preparation of colored composition>

(Coloring composition No. 1)

Pigment (CI Pigment Green 58, trade name: FASTOGEN (registered trademark) GREEN A310, manufactured by DIC Corporation) 18 parts by mass, dispersant composition 12 parts by mass, alkali-soluble resin as binder resin (trade name: Ripox (registered trademark) SPC-2000, Showa Highpolymer Co., Ltd.) 5.4 parts by mass and 64.6 parts by mass of PMA were put into a mixing tank with an inner volume of 500 ml, and stirred for 10 minutes at 2000 rpm using a disper to perform preliminary dispersion. To the obtained pre-dispersion, 640 parts by mass of zirconia beads having a diameter of 0.5 mm were added, followed by stirring at 2000 rpm for 2 hours to carry out main dispersion. 28.5 parts by mass of PMA was 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 Fillter, manufactured by Pall Corporation) to remove zirconia beads. The viscosity and brightness of the obtained colored composition were evaluated. The results are shown in Table 2.

(Coloring composition No. 2 to 8)

Except having changed the dispersant to the one shown in Table 2, coloring composition No. It carried out similarly to the preparation method of 1, and colored composition No. Prepared 2 to 8. Coloring composition No. In 8, the block copolymer obtained above was used as a dispersant.

(Coloring composition No. 9)

Pigment (CI Pigment Blue 15:6, trade name: FASTGEN (registered trademark) Blue A540, manufactured by DIC Corporation) 16 parts by mass, dispersant composition 24 parts by mass, alkali-soluble resin as binder resin (trade name: Ripox (registered trademark) SPC-2000) , Showa Highpolymer Co., Ltd.) 16 parts by mass and 44 parts by mass of PMA were put into a mixing tank with an inner volume of 500 ml, and stirred for 10 minutes at 2000 rpm using a disper to perform preliminary dispersion. To the obtained pre-dispersion, 640 parts by mass of zirconia beads having a diameter of 0.5 mm were added, followed by stirring at 2000 rpm for 2 hours to carry out main dispersion. 33.3 parts by mass of PMA was 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 Fillter, manufactured by Pall Corporation) to remove zirconia beads. The viscosity and brightness of the obtained colored composition were evaluated. The results are shown in Table 2.

(Coloring composition No. 10 to 11)

Except having changed the dispersant to the one shown in Table 2, coloring composition No. It carried out similarly to the preparation method of 9, and colored composition No. 10 and 11 were prepared. Coloring composition No. In 11, the block copolymer obtained above was used as a dispersant.

As a dispersant, dispersant composition No. Coloring composition No. using A to H. 1 to 7, 9, and 10 have high dispersibility of the pigment and low viscosity. Among these, dispersant composition No. containing a cyclic amidine compound as a tertiary amine compound. Coloring composition No. using A to E and H. 1-5, 9, and 10 were also excellent in luminance of the coating film. That is, coloring composition No. 1-5, 9, and 10 are excellent in discoloration resistance even when exposed to high temperature in the manufacturing process of a liquid crystal display, and when a color filter is manufactured using these colored compositions, it can be expected that luminance improves.

The following embodiments are included in this invention.

(Embodiment 1)

(a) Having a block A containing a structural unit derived from a vinyl monomer having an acidic group, and a block B containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) Block copolymer, (b) at least one aromatic compound selected from the group consisting of an aromatic dicarboxylic acid imide, an acidic group-containing aromatic compound and a phenolic hydroxy group-containing aromatic compound, and (c) a tertiary amine compound are mixed Dispersant composition, characterized in that consisting of.

[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 cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion.]

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

(Embodiment 2)

The dispersant composition according to Embodiment 1, wherein the molar ratio of the (a) quaternary ammonium base in the block copolymer and the (b) aromatic compound (quaternary ammonium base in (b)/(a)) is 0.5 to 1.2.

(Embodiment 3)

The dispersant composition according to Embodiment 1 or 2, wherein the molar ratio of the (a) quaternary ammonium base in the block copolymer and the (c) tertiary amine compound (quaternary ammonium base in (c)/(a)) is 0.5 to 1.2 .

(Embodiment 4)

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

(Embodiment 5)

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

(Embodiment 6)

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

[In 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. Further, R ⁶² and R ⁶³ may be bonded to each other to form a cyclic structure.]

[In the general formula (7), R ⁷¹ represents a C 2 to C 6 divalent hydrocarbon group which may have a substituent, and R ⁷² and R ⁷³ are each independently a hydrogen atom or a C 1 to C which may have a substituent It represents 10 hydrocarbon groups. Further, R ⁷² and R ⁷³ may be bonded to each other to form a cyclic structure.]

(Embodiment 7)

A coloring composition containing the dispersant composition, a coloring material, a dispersion medium, and a binder resin in any one of Embodiments 1-6.

(Embodiment 8)

(a) Having a block A containing a structural unit derived from a vinyl monomer having an acidic group, and a block B containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) Block copolymer, (b) at least one aromatic compound selected from the group consisting of an aromatic dicarboxylic acid imide, an acidic group-containing aromatic compound and a phenolic hydroxy group-containing aromatic compound, (c) a tertiary amine compound, a coloring material, dispersion A colored composition comprising a mixture of a medium and a binder resin.

[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 cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion.]

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

(Embodiment 9)

The coloring composition according to Embodiment 7 or 8, wherein the coloring material is a phthalocyanine-based pigment.

(Embodiment 10)

The coloring composition in any one of Embodiments 7-9 which is for color filters.

(Embodiment 11)

A color filter comprising a colored layer formed using the colored composition according to the tenth embodiment.

(Industrial availability)

The block copolymer of the present invention can be used as a dispersant for a coloring material of a colored composition. The coloring composition can be suitably used for color filters. The color filter has high dimensional accuracy and the like, and can be suitably used for a color liquid crystal display element, a color imaging tube element, a color sensor, an organic EL display element, electronic paper, or the like.

Claims (11)

(a) Having a block A containing a structural unit derived from a vinyl monomer having an acidic group, and a block B containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) Block copolymer,
(b) at least one aromatic compound selected from the group consisting of an aromatic dicarboxylic acid imide, an acidic group-containing aromatic compound, and a phenolic hydroxy group-containing aromatic compound, and
(c) A dispersant composition characterized by mixing a tertiary amine compound.

[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 cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion.]

[In formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group.] The method according to claim 1,
The dispersant composition, wherein the molar ratio of the (a) quaternary ammonium base in the block copolymer and the (b) aromatic compound (quaternary ammonium base in (b)/(a)) is 0.5 to 1.2. The method according to claim 1 or 2,
The dispersant composition, wherein the molar ratio of the (a) quaternary ammonium base in the block copolymer and the (c) tertiary amine compound (quaternary ammonium base in (c)/(a)) is 0.5 to 1.2. The method according to any one of claims 1 to 3,
The dispersant composition, wherein the content of the structural unit derived from the vinyl monomer having an acidic group in the block copolymer (a) is 1% by mass to 20% by mass. The method according to any one of claims 1 to 4,
The dispersant composition, wherein the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the block copolymer (a) is 5% by mass to 50% by mass. The method according to any one of claims 1 to 5,
The dispersant composition, wherein the (c) tertiary amine compound is a compound represented by the general formula (6) and/or a compound represented by the general formula (7).

[In 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. Further, R ⁶² and R ⁶³ may be bonded to each other to form a cyclic structure.]

[In the general formula (7), R ⁷¹ represents a C 2 to C 6 divalent hydrocarbon group which may have a substituent, and R ⁷² and R ⁷³ are each independently a hydrogen atom or a C 1 to C which may have a substituent It represents 10 hydrocarbon groups. Further, R ⁷² and R ⁷³ may be bonded to each other to form a cyclic structure.] A colored composition containing the dispersant composition, a coloring material, a dispersion medium, and a binder resin according to any one of claims 1 to 6. (a) Having a block A containing a structural unit derived from a vinyl monomer having an acidic group, and a block B containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) Block copolymer, (b) at least one aromatic compound selected from the group consisting of an aromatic dicarboxylic acid imide, an acidic group-containing aromatic compound and a phenolic hydroxy group-containing aromatic compound, (c) a tertiary amine compound, a coloring material, dispersion A colored composition comprising a mixture of a medium and a binder resin.

[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 cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion.]

[In formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group.] The method according to claim 7 or 8,
The coloring composition, wherein the coloring material is a phthalocyanine-based pigment. The method according to any one of claims 7 to 9,
A coloring composition for a color filter. A color filter comprising a colored layer formed by using the colored composition according to claim 10.