JP2018172530A - Block copolymer, dispersant, coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a block copolymer that is useful as a dispersant for a coloring composition, and gives a coloring composition having a low viscosity and excellent alkali developability.SOLUTION: A block copolymer has A block containing a structural unit represented by the following formula (1) of 60 mass% or more and B block containing a structural unit represented by the following formula (2), and has an acid value of less than 10 mgKOH/g.SELECTED DRAWING: None

Description

  The present invention relates to a block copolymer, and more particularly to a block copolymer that can be used as a pigment dispersant for a coloring composition.

  Conventionally, in the production of color filters used for liquid crystal displays and the like, dyeing methods, printing methods, ink jet methods, electrodeposition methods, pigment dispersion methods, and the like are known as methods for applying a colorant to a substrate. Among these, the pigment dispersion method is the mainstream from the viewpoints of spectral characteristics, durability, pattern shape, and accuracy. In this pigment dispersion method, a coating film made of a colored composition in which a pigment, a dispersant, a dispersion medium (solvent), a binder resin, etc. are mixed is formed on a substrate, and radiation is emitted through a photomask having a desired pattern shape. Irradiation is cured and alkali development is performed. When the alkali developability of the coating film is poor, undeveloped development occurs, and the chromaticity, contrast, dimensional accuracy, etc. of the color filter may be lowered.

  In recent years, in order to obtain good color reproducibility and high contrast of a color filter, studies have been made on increasing the concentration of the pigment in the coloring composition. When the concentration of the pigment is increased, since the proportion of the dispersant is relatively decreased, the dispersant is required to have high dispersibility. In alkali development, a binder resin having alkali solubility plays a major role. However, in the case of a pigment dispersion composition in which the concentration of the pigment is increased, the ratio of the binder resin that is a developing component decreases, and the alkali developability deteriorates. Therefore, the alkali developability originally required for the binder resin is also required for the dispersant.

  As such a dispersant, Patent Document 1 discloses a block composed of an A block having methacrylic acid as a constituent and an acid value of 10 to 150 mgKOH / g and a B block having a methacrylate monomer having an amino group as a constituent. A polymeric dispersant comprising a copolymer is described. This Patent Document 1 describes that alkali developability is improved by the acidic group of the A block (see Patent Document 1 (Claim 1, paragraphs 0034 and 0035)).

  Patent Document 2 discloses an AB block copolymer comprising an A block having a polylactone chain and an acidic group in the side chain, and a B block having a tertiary amino group and a quaternary ammonium base in the side chain. It is described that it is used as a pigment dispersion (see Patent Document 2 (paragraphs 0128 to 0147)). In addition, the block copolymer produced by patent document 2 has an acid value of about 20 mgKOH / g. Moreover, the block copolymer produced by patent document 2 has the content rate of the structural unit which has a polylactone chain in the side chain in A block below 60 mass%.

JP 2013-203887 A JP 2017-19937 A

  In the step of applying the colored composition, if the viscosity of the colored composition is large, the formation efficiency of the coating film is deteriorated and the thickness of the coating film is easily varied. Therefore, the colored composition is required not only to have alkali developability but also to have a low viscosity.

  Here, a copolymer conventionally used as a dispersant has a monomer having an acidic group as a constituent component and adjusts the acid value to 10 to 150 mgKOH / g, thereby improving the alkali developability of the coloring composition. (See Patent Document 1 (paragraph 0035)). However, in such a copolymer having an acid value, when a monomer having a polylactone chain (having an ester bond moiety and a terminal hydroxy group) is introduced in the side chain, the viscosity of the resulting colored composition tends to increase. There is. In this case, there is a problem that the formation efficiency of the coating film is deteriorated and the thickness of the coating film is likely to vary.

  The present invention has been made in view of the above circumstances. For example, when used as a dispersant for a colored composition, the block copolymer can provide a colored composition having a low viscosity and excellent alkali developability. The object is to provide a polymer.

  The block copolymer of the present invention that has been able to solve the above problems includes an A block containing 60% by mass or more of a structural unit represented by the following formula (1), and a structural unit represented by the following formula (2): And an acid value of less than 10 mgKOH / g.

［式（１）において、ｎは１〜１０の整数である。Ｒ¹¹は水素原子またはメチル基である。Ｒ¹²は炭素数が１〜１０のアルキレン基である。Ｒ¹³は炭素数が１〜１０のアルキレン基である。］

[In Formula (1), n is an integer of 1-10. R ¹¹ is a hydrogen atom or a methyl group. R ¹² is an alkylene group having 1 to 10 carbon atoms. R ¹³ is an alkylene group having 1 to 10 carbon atoms. ]

［式（２）において、Ｒ²¹は水素原子またはメチル基を示す。Ｒ²²、Ｒ²³およびＲ²⁴は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ²²、Ｒ²³およびＲ²⁴のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｙ²は２価の連結基を示す。Ｚ^-は対イオンを示す。]

[In the formula (2), R ²¹ represents a hydrogen atom or a methyl group. R ²² , R ²³ and R ²⁴ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ²² , R ²³ and R ²⁴ may be bonded to each other to form a cyclic structure. Y ² represents a divalent linking group. Z ⁻ represents a counter ion. ]

  The block copolymer of the present invention has excellent alkali developability because the A block contains 60% by mass or more of the structural unit represented by the formula (1). Further, the block copolymer of the present invention increases the viscosity of the coloring composition even when the content of the structural unit represented by the formula (1) is increased by controlling the acid value to be less than 10 mgKOH / g. Can be suppressed. Therefore, when used as a dispersant for a colored composition, a colored composition having a low viscosity and excellent alkali developability can be obtained.

  The present invention also includes a dispersant containing the block copolymer. The present invention also includes a color composition containing the dispersant, colorant, dispersion medium, and binder resin, and a color filter including a colored layer formed using the color composition.

  According to the present invention, an object of the present invention is to provide a block copolymer that can give a colored composition having a low viscosity and excellent alkali developability when used as a dispersant for a colored composition.

  Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiments are merely examples. The present invention is not limited to the following embodiments.

<1 block copolymer>
The block copolymer of the present invention has an A block containing 60% by mass or more of a structural unit represented by the following formula (1) and a B block containing a structural unit represented by the following formula (2). The acid value is 10 mgKOH / g or less.

  In the block copolymer of the present invention, since the A block contains 60% by mass or more of the structural unit represented by the formula (1), it has a polylactone chain (an ester bond portion and a terminal hydroxy group) introduced into this side chain. ) Has excellent alkali developability. Here, when the introduction amount of the polylactone chain of the block copolymer used as the dispersant is increased, the presence of acidic groups tends to increase the viscosity of the resulting colored composition. This is considered to be due to the interaction between the polylactone chain and the acidic group. However, the block copolymer of the present invention suppresses an increase in the viscosity of the colored composition by increasing the content of the structural unit represented by the formula (1) and controlling the acid value to less than 10 mgKOH / g. can do. Therefore, when used as a dispersant for a colored composition, a colored composition having a low viscosity and excellent alkali developability can be obtained.

  In the present invention, “A block” can be rephrased as “A segment”, and “B block” can be rephrased as “B segment”. In the present invention, the “vinyl monomer” refers to a monomer having a carbon-carbon double bond capable of radical polymerization in the molecule. The “structural unit derived from a vinyl monomer” refers to a structural unit in which a carbon-carbon double bond capable of radical polymerization of a vinyl monomer is polymerized into a carbon-carbon single bond. “(Meth) acryl” means “at least one of acrylic and methacrylic”. “(Meth) acrylate” means “at least one of acrylate and methacrylate”. “(Meth) acryloyl” refers to “at least one of acryloyl and methacryloyl”.

  Various components of the block copolymer of the present invention will be described below.

(1.1 A block)
The A block is a polymer block containing 60% by mass or more of a structural unit represented by the following formula (1). The structural unit represented by the formula (1) in the A block may be only one type, or may have two or more types. Since the A block has an ester bond moiety and a terminal hydroxy group in the side chain of the structural unit represented by the following formula (1), it has a high affinity for the solvent and the binder resin. Therefore, by using the block copolymer as a dispersant, not only the dispersibility of the pigment but also the alkali developability is improved, and the red precipitate formed from the colored composition is re-dissolved in the solvent. It will be easy.

［式（１）において、ｎは１〜１０の整数である。Ｒ¹¹は水素原子またはメチル基である。Ｒ¹²は炭素数が１〜１０のアルキレン基である。Ｒ¹³は炭素数が１〜１０のアルキレン基である。］

[In Formula (1), n is an integer of 1-10. R ¹¹ is a hydrogen atom or a methyl group. R ¹² is an alkylene group having 1 to 10 carbon atoms. R ¹³ is an alkylene group having 1 to 10 carbon atoms. ]

  N in the formula (1) is preferably an integer of 1 to 7, and more preferably an integer of 1 to 5.

The alkylene group having 1 to 10 carbon atoms represented by R ¹² may be linear or branched, but is preferably linear. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ¹² include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, Nonamethylene group, decamethylene group, 1-methylethylene group and the like can be mentioned. R ¹² is preferably an alkylene group having 1 to 5 carbon atoms.

Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ¹³ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, Nonamethylene group, decamethylene group, etc. are mentioned. R ¹³ is preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 3 to 8 carbon atoms.

As a specific example of the vinyl monomer that forms the structural unit represented by the formula (1), a caprolactone adduct of hydroxyalkyl (meth) acrylate (in formula (1), R ¹³ is a pentamethylene group) is preferable. Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. Among these, 2-hydroxyethyl (meth) acrylate caprolactone adduct (in formula (1), R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an ethylene group, R ¹³ is a pentamethylene group, and n is 1 to 10). ) Is preferred.

  The caprolactone adduct of 2-hydroxyethyl (meth) acrylate includes a 1 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, a 2 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, and 2-hydroxyethyl (meth). Examples include acrylate caprolactone 3 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 4 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 5 mol adduct, and the like.

  The content of the structural unit represented by the formula (1) is 60% by mass or more, preferably 65% by mass or more, more preferably 70% by mass or more, and 90% by mass or less in 100% by mass of the A block. More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less. If the content of the structural unit represented by the formula (1) is 60% by mass or more, the solubility in an alkali solution is improved, the alkali developability is further improved, and if it is 90% by mass or less, a solvent and a binder resin The affinity balance is adjusted, and an increase in the viscosity of the wearing composition is suppressed.

  The A block may have a structural unit other than the structural unit represented by the formula (1). The other structural unit that can be contained in the A block is formed by a vinyl monomer that can be copolymerized with both the vinyl monomer that forms the structural unit represented by the formula (1) and the vinyl monomer that forms the B block described below. There is no particular limitation as long as it is. Vinyl monomers that can form other structural units of the A block may be used alone or in combination of two or more.

  Specific examples of vinyl monomers that can form other structural units of the A block include α-olefins, aromatic vinyl monomers, vinyl monomers containing heterocycles, vinyl amides, vinyl carboxylates, dienes, and (meth) acrylic monomers. Etc. These vinyl monomers may have a hydroxy group or an epoxy group.

Examples of the α-olefin include 1-hexene, 1-octene, 1-decene and the like.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene and the like.
Examples of the vinyl monomer containing a heterocycle include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine and the like.
Examples of the vinylamide include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-captolactam and the like.
Examples of vinyl carboxylate include vinyl acetate, vinyl pivalate, vinyl benzoate and the like.
Examples of dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and the like.

  (Meth) acrylic monomers include (meth) acrylates having a chain alkyl group (straight chain alkyl group or branched chain alkyl group); (meth) acrylates having a cyclic alkyl group (monocyclic structure); aromatic ring groups (Meth) acrylate having (meth) acrylamide; (meth) acrylate having a polyethylene glycol structural unit; (meth) acrylate having a hydroxy group; (meth) acrylate having an alkoxy group; (meth) acrylate having a cyclic ether group, etc. Is mentioned.

  The chain alkyl group of the (meth) acrylate having a chain alkyl group is preferably a chain alkyl group having 1 to 10 carbon atoms, and a linear alkyl group having 1 to 10 carbon atoms is preferable. Specific examples of the (meth) acrylate having a chain alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Examples include sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

  The cyclic alkyl group of the (meth) acrylate having a cyclic alkyl group is preferably a cyclic alkyl group having 6 to 12 carbon atoms. Specific examples of the (meth) acrylate having a cyclic alkyl group include hexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate and the like.

  The aromatic ring of the (meth) acrylate having an aromatic ring group is preferably an aromatic ring having 6 to 12 carbon atoms. Specific examples of the (meth) acrylate having an aromatic ring group include benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like.

  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 polyethylene glycol structural unit include polyethylene glycol (degree of polymerization = 1-5) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization = 1-5) ethyl ether (meth) acrylate, polyethylene glycol ( Degree of polymerization = 1-5) propyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 1-5) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 1-5) ethyl ether (meth) acrylate, polypropylene glycol (Polymerization = 1-5) A propyl ether (meth) acrylate etc. are mentioned.

  As (meth) acrylate having a hydroxy group, hydroxyalkyl such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. (Meth) acrylate etc. are mentioned.

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

  Examples of the (meth) acrylate having a cyclic ether group include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acryloylmorpholine, 2- (4-morpholinyl) ethyl (meth) acrylate, (3- Ethyl oxetane-3-yl) methyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2- [(2-Tetrahydropyranyl) oxy] ethyl (meth) acrylate, 1,3-dioxane- (meth) acrylate and the like.

  The vinyl monomer that can form another structural unit that can be included in the A block is preferably a (meth) acryl monomer, (meth) acrylate having a chain alkyl group, (meth) acrylate having a cyclic alkyl group, aromatic ring group More preferably, it is at least one selected from the group consisting of (meth) acrylates having The vinyl monomer that can be used in the A block can be used alone or in combination of two or more.

  The A block is derived from at least one vinyl monomer selected from the group consisting of a (meth) acrylate having a chain alkyl group, a (meth) acrylate having a cyclic alkyl group, and a (meth) acrylate having an aromatic ring group. In the case of having a structural unit, the total content of these structural units is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and 40% by mass in 100% by mass of A block % Or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less. By being the said range, the balance of the affinity of a solvent and binder resin is arranged, and the raise of the viscosity of a wearing composition is suppressed.

  Moreover, it is preferable that A block does not have an amino group. That is, it is preferable 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 pigment dispersant, the pigment is adsorbed by both the A block and the B block, and the dispersion performance of the pigment is lowered. The content of structural units derived from vinyl monomers having an amino group in the A block (including those in which the amino group is quaternized) is preferably 2% by mass or less, more preferably 1% by mass or less, More preferably, it is 0.1 mass% or less, Most preferably, it is 0 mass%.

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

(1.2 B block)
The B block is a polymer block having a structural unit represented by the following formula (2). The structural unit represented by the formula (2) in the B block may be only one type, or may have two or more types. Since the B block has a quaternary ammonium base in the side chain of the structural unit represented by the following formula (2), it has a high affinity with the pigment.

［式（２）において、Ｒ²¹は水素原子またはメチル基を示す。Ｒ²²、Ｒ²³およびＲ²⁴は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ²²、Ｒ²³およびＲ²⁴のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｙ²は２価の連結基を示す。Ｚ^-は対イオンを示す。]

[In the formula (2), R ²¹ represents a hydrogen atom or a methyl group. R ²² , R ²³ and R ²⁴ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ²² , R ²³ and R ²⁴ may be bonded to each other to form a cyclic structure. Y ² represents a divalent linking group. Z ⁻ represents a counter ion. ]

The chain hydrocarbon group represented by R ^{22 to} R ²⁴ includes both linear and branched chains. Examples of the substituent that the chain hydrocarbon group represented by R ^{22 to} R ²⁴ has include a halogen group, an alkoxy group, a benzoyl group (—COC ₆ H ₅ ), and a hydroxy group. Examples of the substituent that the cyclic hydrocarbon group represented by R ^{22 to} R ²⁴ has include a chain alkyl group, a halogen group, an alkoxy group, and a hydroxy group.

Examples of the group represented by R ^{22 to} R ²⁴ include an optionally substituted alkyl group having 1 to 4 carbon atoms and an optionally substituted aralkyl group having 7 to 16 carbon atoms. A methyl group, an ethyl group, a propyl group, and a benzyl group (—CH ₂ C ₆ H ₅ ) are more preferable.

Examples of the cyclic structure formed by bonding two or more of R ^{22 to} R ²⁴ to each other include a 5- to 7-membered nitrogen-containing heteromonocycle or a condensed ring formed by condensing two of these. . The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring. Specific examples include structures represented by the following formulas (21-1), (21-2), and (21-3).

［式（２１−１）、（２１−２）、（２１−３）において、Ｒ⁶¹は、Ｒ²²〜Ｒ²⁴のいずれかである。Ｒ⁶²は、炭素数１〜６のアルキル基である。ｌは０〜５の整数である。ｍは０〜４の整数である。ｎは０〜４の整数である。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ⁶²は、それぞれ同一でも異なっていてもよい。＊は結合手を示す。］

[In the formulas (21-1), (21-2), and (21-3), R ⁶¹ is any one of R ^{22 to} R ²⁴ . R ⁶² is an alkyl group having 1 to 6 carbon atoms. l is an integer of 0-5. m is an integer of 0-4. n is an integer of 0-4. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ⁶² may be the same or different. * Indicates a bond. ]

In the formula (2), examples of the divalent linking group Y ² include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a —CONH—R ²⁵ — group, a —COO—R ²⁶ — group [ R ²⁵ and R ²⁶ are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms], preferably —COO —R ²⁶ — group, more preferably a —COO—R ²⁷ — group (wherein R ²⁷ is a methylene group or an alkylene group having 2 to 4 carbon atoms).

Examples of Z ⁻ include a halogen anion, an alkyl carboxylate anion, a nitroxide anion, an alkyl sulfate anion, a sulfonate anion, a phosphate anion, and an alkyl phosphate anion.

  Specific examples of the vinyl monomer forming the structural unit represented by the formula (2) include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxypropyltrimethylammonium chloride, (meth) acryloyloxybutyltrimethylammonium chloride. , (Meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxypropylbenzyldimethylammonium chloride, (meth) acryloyloxybutylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride, (meth) acryloyloxy Propylbenzyldiethylammonium chloride, (meth) acryloyloxybutylbenzyldiethyl Ammonium chloride, (meth) acryloyloxyethyltrimethylammonium bromide, (meth) acryloyloxypropyltrimethylammonium bromide, (meth) acryloyloxybutyltrimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium bromide, (meth) acryloyloxypropyl Benzyldimethylammonium bromide, (meth) acryloyloxybutylbenzyldimethylammonium bromide, (meth) acryloyloxyethylbenzyldiethylammonium bromide, (meth) acryloyloxypropylbenzyldiethylammonium bromide, (meth) acryloyloxybutylbenzyldiethylammonium bromide, ( Meta) acryloyloki Ethyltrimethylammonium iodide, (meth) acryloyloxypropyltrimethylammonium 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) a Acryloyloxypropyltrimethylammonium fluoride, (meth) acryloyloxybutyltrimethylammonium fluoride, (meth) acryloyloxyethylbenzyldimethylammonium fluoride, (meth) acryloyloxypropylbenzyldimethylammonium fluoride, (meth) acryloyloxybutyl Examples thereof include benzyldimethylammonium fluoride, (meth) acryloyloxyethylbenzyldiethylammonium fluoride, (meth) acryloyloxypropylbenzyldiethylammonium fluoride, (meth) acryloyloxybutylbenzyldiethylammonium fluoride, and the like.

  The content of the structural unit represented by the formula (2) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and 50% by mass in 100% by mass of the B block. The following is preferable, More preferably, it is 45 mass% or less, More preferably, it is 40 mass% or less. If the content of the structural unit represented by the formula (2) is 10% by mass or more, dispersibility is improved due to strong adsorptivity to the pigment surface, and not only increase in viscosity is suppressed, but also water and alkali Alkali developability is also improved. If the content rate of the structural unit shown by said Formula (2) is 50 mass% or less, the bridging aggregation of the pigments derived from the strong adsorptivity to the pigment surface will be suppressed, and a viscosity increase will be suppressed.

  The B block may have a structural unit represented by the formula (3). The structural unit represented by the formula (3) may be only one type, or may have two or more types.

［式（３）において、Ｒ³¹は水素原子またはメチル基を示す。Ｒ³²およびＲ³³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ³²およびＲ³³が互いに結合して環状構造を形成していてもよい。Ｙ³は２価の連結基を示す。］

[In the formula (3), R ³¹ represents a hydrogen atom or a methyl group. R ³² and R ³³ each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R ³² and R ³³ may be bonded to each other to form a cyclic structure. Y ³ represents a divalent linking group. ]

The chain hydrocarbon group represented by R ³² or R ³³ includes both linear and branched chains. Examples of the substituent that the chain hydrocarbon group represented by R ³² or R ³³ has include a halogen group, an alkoxy group, a benzoyl group, and a hydroxy group. Examples of the substituent that the cyclic hydrocarbon group represented by R ³² or R ³³ has include a chain alkyl group, a halogen group, an alkoxy group, and a hydroxy group.

Examples of the group represented by R ³² or R ³³ include an optionally substituted alkyl group having 1 to 4 carbon atoms and an optionally substituted aralkyl group having 7 to 16 carbon atoms. A methyl group, an ethyl group, a propyl group, and a benzyl group are more preferable.

Examples of the cyclic structure formed by bonding R ³² or R ³³ to each other include a 5- to 7-membered nitrogen-containing heteromonocycle or a condensed ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring. Specific examples include structures represented by the following formulas (31-1), (31-2), and (31-3).

［式（３１−１）、（３１−２）、（３１−３）において、Ｒ⁷¹は、炭素数１〜６のアルキル基である。ｌは０〜５の整数である。ｍは０〜４の整数である。ｎは０〜４の整数である。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ⁷¹は、それぞれ同一でも異なっていてもよい。＊は結合手を示す。］

[In the formulas (31-1), (31-2), and (31-3), R ⁷¹ represents an alkyl group having 1 to 6 carbon atoms. l is an integer of 0-5. m is an integer of 0-4. n is an integer of 0-4. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ⁷¹ may be the same or different. * Indicates a bond. ]

In the formula (3), examples of the divalent linking group Y ³ include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a —CONH—R ³⁴ — group, a —COO—R ³⁵ — group [ R ³⁴ and R ³⁵ are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms], preferably —COO —R ³⁵ — group, and —COO—R ³⁶ — group (where R ³⁶ is a methylene group, an alkylene group having 2 to 4 carbon atoms) is more preferred.

  Specific examples of the vinyl monomer forming the structural unit represented by the formula (3) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) ) Acrylate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate and the like.

  The content of the structural unit represented by the formula (3) is preferably 50% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, and 90% by mass in 100% by mass of the B block. The following is preferable, More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less.

  The B block may be only the structural unit represented by formula (2) and the structural unit represented by formula (3), or may contain other structural units. From the viewpoint of maintaining the affinity with the pigment, the total content of the structural unit represented by the formula (2) and the structural unit represented by the formula (3) in the B block is preferably 80% by mass or more, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more. The structural unit represented by the formula (2) has a quaternary ammonium base in the side chain, and the structural unit represented by the formula (3) has a tertiary amino group in the side chain. By setting the quaternary ammonium base and the tertiary amino group in the above ranges, strong adsorptivity to the pigment surface can be maintained for a long time, and the storage stability of the coloring composition is improved.

  Moreover, it is preferable that B block does not contain the structural unit represented by Formula (1) substantially. That is, the content of the structural unit represented by the formula (1) is preferably 5% by mass or less, and more preferably 2% by mass or less in 100% by mass of the B block.

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

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

(1.3 Block copolymer)
The structure of the block copolymer is preferably a linear block copolymer. The linear block copolymer may have any structure (arrangement). From the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the A block is A and the B block is B. when expressed as, (a-B) _m type, (a-B) _m -A type, the group consisting of (B-a) _m -B type (m is an integer of 1 or more, for example, an integer of 1 to 3) It is preferably a copolymer having at least one structure selected from Among these, a diblock copolymer represented by AB is preferable from the viewpoint of handleability during processing and physical properties of the composition. By constituting the diblock copolymer represented by AB, the structural unit represented by the formula (1) in the A block and the structural unit represented by the formula (2) in the B block When localized and the block copolymer of the present invention is used in a colored composition, it is considered that the pigment, the solvent, and the binder resin (alkali-soluble resin) can be efficiently operated suitably.

  The content of the A block is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and preferably 90% by mass or less, in 100% by mass of the entire block copolymer. More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less. The content of the B block is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 50% by mass or less, in 100% by mass of the entire block copolymer. More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less. By adjusting the content ratios of the A block and the B block within the above range, the dispersion performance and the alkali developability when used as a dispersant can be balanced.

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

  The content of the structural unit represented by the formula (1) is preferably 40% by mass or more, more preferably 45% by mass or more, and still more preferably 50% by mass or more, in 100% by mass of the entire block copolymer. 80 mass% or less, more preferably 70 mass% or less, still more preferably 60 mass% or less.

  The total content of the structural unit represented by the formula (2) and the structural unit represented by the formula (3) is preferably 10% by mass or more, more preferably 20% by mass in 100% by mass of the entire block copolymer. % Or more, more preferably 25% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less.

  The molecular weight of the block copolymer of the present invention is measured by gel permeation chromatography (hereinafter referred to as “GPC”) method. The block copolymer preferably has a weight average molecular weight (Mw) of 5000 or more, more preferably 6000 or more, further preferably 7000 or more, preferably 15000 or less, more preferably 12000 or less, and still more preferably 10,000 or less. . When the weight average molecular weight is within the above range, the dispersion performance when used as a dispersant becomes better.

  The molecular weight distribution (PDI) of the block copolymer of the present invention is preferably 2.0 or less, and more preferably 1.6 or less. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.0, one having a low molecular weight or one having a high molecular weight is included.

  The amine value of the block copolymer of the present invention is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 30 mgKOH / g or more, from the viewpoint of the adsorptivity to the pigment and the pigment dispersibility. 250 mgKOH / g or less is preferable, more preferably 200 mgKOH / g or less, still more preferably 150 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less. The amine value can be adjusted by the content of the structural unit represented by the formula (3).

  The acid value of the block copolymer of the present invention is less than 10 mgKOH / g, more preferably 5 mgKOH / g or less, still more preferably 3 mgKOH / g or less. The acid value is derived from the structural unit having an acidic group. However, when the acid value exceeds the above range, the viscosity of the colored composition increases, and the increase in the viscosity is particularly remarkable when the content of the quaternary ammonium base increases. Therefore, it is not preferable. Conventionally, it is known that a dispersant composed of a polymer having an amino group or a quaternary ammonium base in the side chain further improves the alkali developability of the colored composition by further having an acidic group in the side chain. However, the reason is not clear, but the block copolymer of the present invention does not have an acidic group, so that the viscosity of the colored composition is lowered and the alkali developability can be improved.

<Method for producing 2-block copolymer>
As a method for producing the block copolymer of the present invention, a method in which an A block is first produced by a polymerization reaction of a vinyl monomer, and a monomer in a B block is polymerized into the A block; A method of polymerizing A block monomers; A block and B block are prepared separately, and then the A block and B block are coupled; the A block is prepared first, and the A block is represented by the formula (3) A monomer composition containing a vinyl monomer capable of forming a structural unit represented by the formula A monomer composition containing a vinyl monomer capable of forming the structural unit represented by the formula (3), polymerizing an A-block monomer into the polymer, Method of quaternizing a part of the tertiary amine structure of the structural unit represented by (3); A block and a block having the structural unit represented by the formula (3) are produced separately, and these blocks And a method of quaternizing a tertiary amine structure of a part of the structural unit represented by the formula (3) in the obtained polymer.

  When the tertiary amine group of the structural unit represented by the formula (3) is quaternized, examples of the quaternizing agent include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide; benzyl chloride Aralkyl halides such as benzyl bromide and benzyl iodide; dimethyl sulfate; dialkyl sulfates such as diethyl sulfate and di-n-propyl sulfate; and the like. Among these, aralkyl halides such as benzyl chloride, benzyl bromide and benzyl iodide are preferable, and benzyl chloride is more preferable. In the structure after quaternization, an alkyl group and an aralkyl group derived from a quaternizing agent are introduced. Therefore, the amount of the structural unit represented by the formula (2) can be estimated by measuring the amount of the alkyl group and aralkyl group introduced by quaternization.

  Examples of a method for quaternizing a tertiary amine structure of a part of the structural unit represented by the formula (3) in the polymer include a method of bringing the polymer and a quaternizing agent into contact with each other. Specifically, there is a method in which a monomer composition containing a vinyl monomer capable of forming the structural unit represented by the formula (3) is polymerized, and then a quaternizing agent is added to the reaction solution and stirred. . The temperature of the reaction solution to which the quaternizing agent is added is preferably 55 ° C. to 65 ° C., and the stirring time is preferably 5 hours to 20 hours. When adding the quaternizing agent, it is also preferable to dilute the reaction solution after polymerization. Examples of the solvent to be added for dilution include a solvent that can be used for the polymerization reaction, a protic solvent is preferable, and methanol is more preferable.

  The method for polymerizing the vinyl monomer is not particularly limited, but living radical polymerization is preferred. That is, the block copolymer used in the present invention is preferably a polymer obtained by polymerization using living radical polymerization. In the conventional radical polymerization method, not only the initiation reaction and the growth reaction, but also the termination of the growth end occurs due to the termination reaction and the chain transfer reaction, and the polymer tends to be a mixture of polymers having various molecular weights and heterogeneous compositions. While the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method, the termination reaction and chain transfer are unlikely to occur, and the growth end grows without being deactivated. This is preferable in that it is easy to produce a polymer having a uniform composition.

  In the living radical polymerization method, a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); There is a method to be used (TERP method). Since the ATRP method uses an amine-based complex, it may not be used unless the acidic group of the vinyl monomer having an acidic group is protected. In the RAFT method, when various monomers are used, it is difficult to obtain a low molecular weight distribution, and there may be a problem such as sulfur odor or coloring. Among these methods, the TERP method is preferably used from the viewpoints of diversity of usable monomers, molecular weight control in the polymer region, uniform composition, or coloring.

  The TERP method is a method of polymerizing a radical polymerizable compound (vinyl monomer) using an organic tellurium compound as a polymerization initiator. For example, International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and WO 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d).
(A) A method in which a vinyl monomer is polymerized using an organic tellurium compound represented by the formula (4).
(B) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by formula (4) and an azo polymerization initiator.
(C) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by formula (4) and an organic ditellurium compound represented by formula (5).
(D) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by formula (4), an azo polymerization initiator, and an organic ditellurium compound represented by formula (5).

［式（４）において、Ｒ⁴¹は、炭素数１〜８のアルキル基、アリール基または芳香族ヘテロ環基である。Ｒ⁴²およびＲ⁴³は、それぞれ独立に、水素原子または炭素数１〜８のアルキル基である。Ｒ⁴⁴は、炭素数１〜８のアルキル基、アリール基、置換アリール基、芳香族ヘテロ環基、アルコキシ基、アシル基、アミド基、オキシカルボニル基、シアノ基、アリル基またはプロパルギル基である。］

[In the formula (4), R ⁴¹ is an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms. R ⁴² and R ⁴³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴⁴ is an alkyl group having 1 to 8 carbon atoms, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, acyl group, amide group, oxycarbonyl group, cyano group, allyl group or propargyl group. ]

［式（５）において、Ｒ⁴¹は、炭素数１〜８のアルキル基、アリール基または芳香族ヘテロ環基である。］

[In formula (5), R ⁴¹ is an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms. ]

The group represented by R ⁴¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group, and is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. And a linear or branched alkyl group such as a octyl group and a cyclic alkyl group such as a cyclohexyl group. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.

The groups represented by R ⁴² and R ⁴³ 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 group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. And a linear or branched alkyl group such as a octyl group and a cyclic alkyl group such as a cyclohexyl group. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.

The group represented by R ⁴⁴ is a C 1-8 alkyl group, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, acyl group, amide group, oxycarbonyl group, cyano group, allyl group or A propargyl group, specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. And a linear or branched alkyl group such as an octyl group, a cyclic alkyl group such as a cyclohexyl group, and the like. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group. A phenyl group is preferred.
Examples of the substituted aryl group include a phenyl group having a substituent and a naphthyl group having a substituent. Examples of the substituent of the aryl group having a substituent include a halogen atom, a hydroxy group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by —COR ⁴⁴¹ (R ⁴⁴¹ is a carbon number) 1-8 alkyl group, aryl group, C1-C8 alkoxy group or aryloxy group), sulfonyl group, trifluoromethyl group and the like. These substituents are preferably substituted by 1 or 2 substituents.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tet- A butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and the like can be given.
Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
Examples of the amide group include —CONR ⁴⁴²¹ R ⁴⁴²² (R ⁴⁴²¹ and R ⁴⁴²² 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 ⁴⁴³ (R ⁴⁴³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group) is preferable. Group, n-butoxycarbonyl group, sec-butoxycarbonyl group, ter-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group and the like. Preferred oxycarbonyl groups include methoxycarbonyl group and ethoxycarbonyl group.
As the allyl group, —CR ⁴⁴⁴¹ R ⁴⁴⁴² —CR ⁴⁴⁴³ = CR ⁴⁴⁴⁴ R ⁴⁴⁴⁵ (R ⁴⁴⁴¹ and R ⁴⁴⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁴⁴³ , R ⁴⁴⁴⁴ and R ⁴⁴⁴⁵ are Are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and each substituent may be linked by a cyclic structure).
As the propargyl group, —CR ⁴⁴⁵¹ R ⁴⁴⁵² —C≡CR ⁴⁴⁵³ (R ⁴⁴⁵¹ and R ⁴⁴⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁴⁵³ is a hydrogen atom and an alkyl group having 1 to 8 carbon atoms) , Aryl group or silyl group).

  Specific examples of the organic tellurium compound represented by the formula (4) include (methylterranylmethyl) benzene, (methylterranylmethyl) naphthalene, ethyl-2-methyl-2-methylterranyl-propionate, and ethyl-2-methyl. -2-n-butyl terranyl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methyl terranyl-propionate, (2-hydroxyethyl) -2-methyl-2-methyl terranyl-propionate or (3-trimethylsilylpropargyl) 2-methyl-2-methylterranyl-propinate, etc. Organic tellurium described in International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and International Publication No. 2004/096870 Illustrate all of the compounds Can.

  Specific examples of the organic ditellurium compound represented by the formula (5) include dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, dicyclopropylditelluride, -N-butyl ditelluride, di-s-butyl ditelluride, di-t-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis Examples include-(p-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride or dipyridyl ditelluride.

  The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal 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-methylbutyramide), 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile) (V-70), 2,2′-azobis (2-methylamidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propyl Pan], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2-cyano-2-propyl Examples include azoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), and the like.

  In the polymerization methods (a), (b), (c) and (d), the amount of vinyl monomer used may be appropriately adjusted depending on the physical properties of the target copolymer. It is preferable to make vinyl monomers into 5 mol to 10000 mol with respect to 1 mol of the organic tellurium compound.

  In the polymerization method (b), when the organic tellurium compound of the formula (4) and the azo polymerization initiator are used in combination, the amount of the azo polymerization initiator used is usually the organic tellurium compound of the formula (4). The azo polymerization initiator is preferably 0.01 mol to 10 mol with respect to 1 mol.

  In the polymerization method of (c), when the organic tellurium compound of formula (4) and the organic ditellurium compound of formula (5) are used in combination, the amount of the organic ditellurium compound of formula (5) is usually The organic ditellurium compound of the formula (5) is preferably 0.01 mol to 100 mol with respect to 1 mol of the organic tellurium compound 4).

  In the polymerization method (d), when the organic tellurium compound of the formula (4), the organic ditellurium compound of the formula (5) and the azo polymerization initiator are used in combination, the amount of the azo polymerization initiator used is usually The azo polymerization initiator is preferably 0.01 mol to 100 mol with respect to 1 mol in total of the organic tellurium compound of formula (4) and the organic ditellurium compound of formula (5).

  The polymerization reaction can be carried out without a solvent, but it may be carried out using an aprotic solvent or a protic solvent generally used in radical polymerization and stirring the mixture. Examples of aprotic solvents that can be used include benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, hexafluoroisopropol, propylene glycol monomethyl. Examples include ether acetate, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate, trifluoromethylbenzene, and the like. Examples of the protic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

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

  The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the copolymer to be obtained, but are usually 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.

  After completion of the polymerization reaction, the desired copolymer can be separated from the obtained reaction mixture by a usual separation and purification means.

The growth terminal of the copolymer obtained by the polymerization reaction is in the form of -TeR ⁴¹ (wherein R ⁴¹ is the same as described above), and it is deactivated by the operation in the air after the completion of the polymerization reaction. , Tellurium atoms may remain. Since the copolymer in which the tellurium atom remains at the terminal is colored or inferior in thermal stability, it is preferable to remove the tellurium atom.

  As a method for removing tellurium atoms, a radical reduction method using tributylstannane or a thiol compound; a method of adsorbing with activated carbon, silica gel, activated alumina, activated clay, molecular sieves, polymer adsorbent, etc .; Method of adsorbing metal: Add peroxide such as hydrogen peroxide or benzoyl peroxide, or blow air or oxygen into the system to oxidatively decompose tellurium atoms at the end of the copolymer. A liquid-liquid extraction method or solid-liquid extraction method that removes residual tellurium compounds by combining solvents; a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less can be used. These methods can also be used in combination.

<Dispersant>
The dispersant of the present invention contains the block copolymer as a main component. In the block copolymer, for example, a 3 amino group and a quaternary ammonium base in the structure (B block) are firmly bonded to an acidic group of a pigment treated with an acidic pigment or an acidic group-containing dye derivative. It is considered that the B block adsorbs to the pigment, thereby exhibiting an effect of improving the pigment dispersibility. That is, the dispersant of the present invention is a component that favorably disperses the colorant by this action, and therefore the type of the colorant to be dispersed is not particularly limited.

<Coloring composition>
The coloring composition of this invention contains the said dispersing agent, a coloring agent, a dispersion medium, and binder resin.

  Various components of the colored composition of the present invention will be described below.

(Coloring agent)
The type and particle size of the colorant may be appropriately selected depending on the application and are not particularly limited. The colored composition preferably contains a pigment as a colorant. The pigment may be either an organic pigment or an inorganic pigment, but an organic pigment mainly composed of an organic compound is particularly preferable. Examples of the pigment include pigments of various colors such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, and a purple pigment. 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, indigo Examples thereof include polycyclic pigments such as pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments. The pigment contained in the coloring composition may be only one type or a plurality of types.

  Specific examples of the pigment include C.I. 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, 168, 177, Red pigments such as 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264; 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, 188, 193, 194, 213; I. Orange pigments such as CI Pigment Orange 36, 38, 43; I. Pigment Blue 15, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60 and the like; C.I. I. Green pigments such as Pigment Green 7, 36, 58; I. And purple pigments such as Pigment Violet 23, 32, and 50. Among these pigments, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58 and the like are preferable.

  In the present invention, the dispersant is C.I. I. Pigment Red 254, C.I. I. It is preferably used with a colorant containing a diketopyrrolopyrrole pigment such as Pigment Red 255.

  The upper limit of the content of the colorant in the coloring composition is usually 80% by mass, preferably 70% by mass, and preferably 60% by mass in the total solid content of the coloring composition from the viewpoint of luminance. It is more preferable. Further, the lower limit of the content of the colorant in the coloring composition is usually 10% by mass, preferably 20% by mass, and more preferably 30% by mass in the total solid content of the coloring composition. preferable. Here, solid content is components other than the dispersion medium mentioned later.

(Dispersion medium)
The colored composition of the present invention is suitably used as a dispersion medium as long as it disperses or dissolves other components constituting the colored composition and does not react with these components and has moderate volatility. You can select and use. For example, conventionally known organic solvents can be used, such as 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, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Monomethyl ether, 3-methyl- -Glycol monoalkyl ethers such as methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether Glycol dialkyl ethers such as 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 Teracetate, 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 -Glycol alkyl ether acetates such as n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate; ethylene glycol Glycol diacetates such as diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether , Ethers such as butyl ether, diamyl ether, ethyl isobutyl ether, 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, Ketones such as methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone; Monovalent or polyhydric alcohols such as diol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, methoxymethylpentanol, glycerin, and benzyl alcohol 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, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, acetic acid Mill, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, 3 -Chain or cyclic esters such as ethyl ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate and γ-butyrolactone; 3-methoxypropion Acids, alkoxycarboxylic acids such as 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; acetonitrile, benzonitrile, etc. Nitriles and the like.

  The organic solvent is preferably glycol alkyl ether acetates, monovalent or polyhydric alcohols from the viewpoints of dispersibility of the colorant and the like, solubility of the dispersant, coatability of the colored composition, and the like. The solvent contained in the coloring composition may be only one type or a plurality of types.

  Content of the dispersion medium in a coloring composition is not specifically limited, It can adjust suitably. The upper limit of the content of the dispersion medium in the coloring composition is usually 99% by mass. Further, the lower limit of the content of the dispersion medium in the colored composition is usually 70% by mass and preferably 75% by mass in consideration of the 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 coloring composition.

(Binder resin)
The colored composition of the present invention contains a binder resin (excluding the dispersant). Thereby, the alkali developability of a coloring composition and the binding property to a board | substrate can be improved. Such a binder resin is not particularly limited, but is preferably a resin having an acidic group such as a carboxy group or a phenolic hydroxy group.

  The binder resin is preferably a random copolymer containing a structural unit derived from a carboxy group-containing vinyl monomer and a structural unit derived from a (meth) acrylic acid ester. As the carboxy group-containing vinyl monomer, (meth) acrylic acid is preferable. Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate.

  In the binder resin, the total content of the structural unit derived from the carboxy group-containing vinyl monomer and the structural unit derived from the (meth) acrylic acid ester is preferably 50% by mass or more, more preferably 60% by mass or more, Preferably it is 70 mass% or more. Further, the binder resin preferably has a structure content derived from a carboxy group-containing vinyl monomer of 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 more preferable, and 70% by mass or less is more preferable.

  Among these, a random copolymer of a carboxy group-containing vinyl monomer and a (meth) acrylic acid ester is preferable. 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, Examples include random copolymers of (meth) acrylic acid, butyl (meth) acrylate, and benzyl (meth) acrylate. From the viewpoint of the affinity between the binder resin and the colorant, the binder resin is particularly preferably a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate.

  In the copolymer of a carboxy group-containing vinyl monomer and a (meth) acrylic acid ester, the content of (meth) acrylic acid is usually 5% by mass to 90% by mass, and 10% by mass to 70% in all monomer components. It is preferable that it is mass%, and it is more preferable that it is 20 mass%-70 mass%.

  The Mw of the binder resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 20,000. When the Mw of the binder resin is 3,000 or more, the heat resistance, film strength, etc. of the colored layer formed from the colored composition are improved, and when the Mw is 100,000 or less, the coating film has an alkaline aqueous solution. The developability becomes even better.

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

  The binder resin contained in the coloring composition may be only one type or a plurality of types. In the pigment dispersion composition, the content of the binder resin is preferably 5 parts by mass to 200 parts by mass, and more preferably 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the colorant. More preferably, it is 80 parts by mass.

(Crosslinking agent)
The coloring composition of the present invention may contain a crosslinking agent. A cross-linking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. 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.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional compound modified with caprolactone ( (Meth) acrylate, polyfunctional (meth) acrylate modified with alkylene oxide, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate having hydroxy group and polyfunctional isocyanate, (meth) acrylate having hydroxy group And a polyfunctional (meth) acrylate having a carboxy group obtained by reacting an acid anhydride with the acid anhydride.

  Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; trivalent or more such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Of the aliphatic polyhydroxy compound. Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and di Examples include pentaerythritol hexa (meth) acrylate and glycerol dimethacrylate. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride; pyromellitic anhydride, biphenyltetracarboxylic acid And tetrabasic acid dianhydrides such as acid 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 colorant. If the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the amount of the crosslinking agent is too large, the alkali developability of the colored composition of the present invention is lowered, and background stains, film residues, etc. tend to occur on the unexposed portion of the substrate or on the light shielding layer. .

(Photopolymerization initiator)
The coloring composition of the present invention preferably contains a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of a crosslinking agent upon exposure to radiation such as visible light, ultraviolet light, far infrared light, electron beam, and X-ray.

  Examples of the photopolymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketones. Compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and the like. A photoinitiator 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, particularly preferably 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, curing may be insufficient due to exposure. On the other hand, if the content is too large, the formed colored layer tends to easily fall off from the substrate during development. .

(Other ingredients)
The coloring composition of the present invention may further contain an acidic dye derivative having an acidic group in order to adsorb the amino composition in the block copolymer that characterizes the present invention used as a dispersant by ion bonding. preferable. This dye derivative has an acidic functional group introduced into the dye skeleton. As the dye skeleton, the same or similar skeleton as the colorant constituting the coloring composition and the same or similar skeleton as the compound used as the raw material of the pigment are preferable. Specific examples of the dye skeleton include azo dye skeleton, phthalocyanine dye skeleton, anthraquinone dye skeleton, triazine dye skeleton, acridine dye skeleton, and perylene dye skeleton. The acidic group introduced into the dye skeleton is preferably a carboxy group, a phosphoric acid group, or a sulfonic acid group. In addition, a sulfonic acid group is preferable from the viewpoint of synthesis and the strength of acidity. The acidic group may be directly bonded to the dye skeleton, but may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, ether, sulfonamide, or urethane bond.

<Manufacturing method of coloring composition and color filter>
The coloring composition contains a coloring agent, a dispersing agent, a dispersing medium, a binder resin, and a crosslinking agent, a photopolymerization initiator, and other additives as necessary. For example, a paint shaker, a bead mill, a ball mill, a dissolver, a kneader It is manufactured by mixing using a mixing and dispersing machine such as. The coloring composition is preferably filtered after mixing. Examples of other additives include pH adjusters, antioxidants, ultraviolet absorbers, light stabilizers, preservatives, and fungicides.

  Since the colored composition of the present invention has a low viscosity and excellent alkali developability, it can be suitably used for a color filter.

  The color filter of this invention is provided with the colored layer formed using the said coloring composition. Examples of the method for producing the color filter include the following methods. First, for example, after applying the coloring composition of the present invention in which a red pigment is dispersed on a substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement. Then, using each colored composition of green or blue, and applying each colored composition, pre-baking, exposing, developing, and post-baking in the same manner as described above, the green pixel array and the blue pixel array are formed on the same substrate. Sequentially formed on top. Thereby, a color filter in which a pixel array of the three primary colors of red, green and blue is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

When applying the coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, etc. can be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.
A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter.

  The color filter of the present invention has high dimensional accuracy 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, and the like.

  Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples, and can be implemented with appropriate modifications without departing from the scope of the invention. The polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI), amine value and acid value of the dispersant and binder resin, and the viscosity and alkali developability of the colored composition were evaluated according to the following methods.

The abbreviations have the following meanings.
BTEE: ethyl-2-methyl-2-n-butylterranyl-propionate DBDT: dibutylditelluride AIBN: 2,2′-azobis (isobutyronitrile)
BMA: butyl methacrylate PCL5: 5-mol caprolactone adduct of 2-hydroxyethyl methacrylate (manufactured by Daicel Chemical Industries, Plaxel (registered trademark) FM5)
DMAEMA: dimethylaminoethyl methacrylate BzCl: benzyl chloride MAA: methacrylic acid BzMA: benzyl methacrylate PMA: propylene glycol monomethyl ether acetate MeOH: methanol

(Polymerization rate)
¹ H-NMR was measured (solvent: CDCl ₃ , internal standard: TMS) using a nuclear magnetic resonance (NMR) measuring apparatus (Bruker BioSpin, model: AVANCE500 (frequency: 500 MHz)). About the obtained NMR spectrum, the integration 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 determined, and the polymerization rate of the monomer was calculated.

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))
It calculated | required from the gel permeation chromatography (GPC) using the high performance liquid chromatograph (The Tosoh make, model HLC-8320). As for the column, one SHODEX KF-603 (φ6 mm × 150 mm) (manufactured by SHODEX), 10 mmol / L lithium bromide / 10 mmol / L acetic acid / N-methyl-2-pyrrolidone solution as a mobile phase, and differential refractometer as a detector It was used. The measurement conditions were a column temperature of 40 ° C., a sample concentration of 10 mg / mL, a sample injection amount of 10 μm, 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 this measured value. In addition, about the block copolymer (block copolymer No. 8-11) which used the acidic group containing monomer for the raw material monomer, a few drops of methanol and trimethylsilyldiazomethane were added as a pretreatment of GPC measurement, and methyl esterification reaction Then, GPC measurement was performed.

(Amine number)
The amine value represents the mass of potassium hydroxide (KOH) equivalent to the basic component per gram 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 amine value (B) was calculated by the following formula using the inflection point of the titration pH curve as the titration end point.
B = 56.11 × Vs × 0.1 × f / w
B: Amine value (mgKOH / g)
Vs: Amount of 0.1 mol / L hydrochloric acid / 2-propanol solution required for titration (mL)
f: titer of 0.1 mol / L hydrochloric acid (2-propanol) w: mass (g) of measurement sample (solid content conversion)

(Acid value)
The acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content. A measurement sample was dissolved in tetrahydrofuran, and a few drops of 1.0 w / v% phenolphthalein ethanol (90) solution was added as an indicator to the resulting solution, followed by neutralization titration with a 0.1 mol / L potassium hydroxide / ethanol solution. . The acid value was calculated according to the following formula, with a little redness remaining as the titration end point.
A = 56.11 × Vs × 0.1 × f / w
A: Acid value (mgKOH / g)
Vs: Amount of 0.1 mol / L potassium hydroxide / ethanol solution used for titration (mL)
f: 0.1 mol / L potassium hydroxide / ethanol solution titer w: measurement sample mass (g) (solid content conversion)

(viscosity)
Using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.), a cone rotor (1 ° 34 ′ × R24) was used, and the viscosity was measured at 25 ° C. and a rotor rotational speed of 60 rpm.

(Alkali developability)
Using a spin coater (trade name: MS-A100, manufactured by Mikasa Co., Ltd.) on a 50 mm × 50 mm glass plate whose surface has been cleaned, a coating film of the colored composition is formed at 2000 rpm for 5 seconds. Dried for minutes. Next, the glass plate on which the coating film is formed is immersed in a 0.1% aqueous potassium hydroxide solution, and the glass plate is pulled up with a dip coater (trade name: DC4016, manufactured by Aiden) (speed 0.22 mm / s), The alkali developability was evaluated by the time until the coating film was dissolved.

<Manufacture of block copolymer>
(Production Example 1: Block copolymer No. 1)
PCL5 (299.2 g), BMA (99.8 g), AIBN (2.46 g), PMA (266.0 g) were charged into a flask equipped with an argon gas introduction tube and a stirrer, and after substitution with argon, BTEE (22 .48 g) and DBDT (13.84 g) were added and reacted at 60 ° C. for 20 hours to polymerize the A block. The polymerization rate was 100%.

  To the reaction solution, a mixed solution of DMAEMA (125.8 g), AIBN (1.23 g), PMA (83.9 g) previously substituted with argon was added and reacted at 60 ° C. for 25 hours to polymerize the B block. The polymerization rate was 99%.

  After completion of the reaction, the reaction solution was diluted with MeOH (495 g) previously substituted with argon, and BzCl (10.1 g) was added to the diluted solution, followed by reaction at 60 ° C. for 12 hours for quaternization.

  After completion of the reaction, it was poured into stirred n-heptane. The precipitated polymer was suction filtered and dried to obtain a block copolymer No. 1 was obtained. The obtained block copolymer No. 1 had an Mw of 11027, a PDI of 1.33, an acid value of less than 3 mgKOH / g, and an amine value of 72 mgKOH / g.

(Production Examples 2 to 7: Block copolymer Nos. 2 to 7)
Block copolymer No. In the same manner as in the production method of No. 1, block copolymer No. 2-7 were produced. Table 1 shows the raw material monomers, organic tellurium compounds, organic ditellurium compounds, azo polymerization initiators, solvents, quaternizing agents, reaction conditions, and polymerization rate used. Table 2 shows the composition, Mw, PDI, acid value, and amine value of each block copolymer.

(Comparative Production Example 1: Block copolymer No. 8)
PCL5 (137.9 g), BMA (42.3 g), MAA (3.7 g), AIBN (0.82 g), PMA (120.1 g) were charged into a flask equipped with an argon gas introduction tube and a stirrer. After argon substitution, BTEE (7.49 g) and DBDT (4.61 g) were added and reacted at 60 ° C. for 20 hours to polymerize the A block. The polymerization rate was 100%.

  To the reaction solution, a mixed solution of DMAEMA (58.0 g), AIBN (0.41 g), and PMA (38.6 g) previously substituted with argon was added and reacted at 60 ° C. for 9 hours to polymerize the B block. The polymerization rate was 96%.

  After completion of the reaction, the reaction solution was diluted with MeOH (230 g) previously substituted with argon, and BzCl (4.7 g) was added to the diluted solution, followed by reaction at 60 ° C. for 12 hours for quaternization.

  After completion of the reaction, it was poured into stirred n-heptane. The precipitated polymer was suction filtered and dried to obtain a block copolymer No. 8 was obtained. The obtained block copolymer No. 8 had an Mw of 9760, a PDI of 1.23, an acid value of 18 mgKOH / g, and an amine value of 71 mgKOH / g.

(Comparative Production Examples 2 and 3: Block copolymer Nos. 9 and 10)
Block copolymer No. In the same manner as in the production method of No. 8, block copolymer No. 9 and 10 were produced. Table 1 shows the raw material monomers, organic tellurium compounds, organic ditellurium compounds, azo polymerization initiators, solvents, quaternizing agents, reaction conditions, and polymerization rate used. Table 2 shows the composition, Mw, PDI, acid value, and amine value of each dispersant.

(Comparative Production Example 4: Block copolymer No. 11)
PCL5 (137.9 g), BMA (38.6 g), MAA (7.4 g), AIBN (0.82 g), PMA (117.7 g) were charged into a flask equipped with an argon gas introduction tube and a stirrer. After substitution with argon, BTEE (7.49 g) and DBDT (4.61 g) were added and reacted at 60 ° C. for 13 hours to polymerize the A block. The polymerization rate was 100%.

  To the reaction solution, a mixed solution of DMAEMA (58.0 g), AIBN (0.41 g), and PMA (38.6 g) previously substituted with argon was added and reacted at 60 ° C. for 10 hours to polymerize the B block. The polymerization rate was 99%.

  After completion of the reaction, it was poured into stirred n-heptane. The precipitated polymer was suction filtered and dried to obtain a block copolymer No. 11 was obtained. The obtained block copolymer No. 11 had an Mw of 9230, a PDI of 1.15, an acid value of 23 mgKOH / g, and an amine value of 84 mgKOH / g.

<Manufacture of coloring composition>
(Manufacture of binder resin)
A flask equipped with an argon gas introduction tube and a stirrer was charged with MAA (20.0 g), BzMA (80.0 g), and PMA (290.0 g). After purging with argon, AIBN (1.5 g), n-dodecane Thiol (2.0 g) and PMA (10.0 g) were added and the temperature was raised to 90 ° C. While maintaining the solution at 90 ° C., MAA (40.0 g), BzMA (160.0 g), AIBN (3.0 g), n-dodecanethiol (4.0 g) and PMA (25.0 g) were added to the solution. It was added dropwise over 1.5 hours. Sixty minutes after the completion of dropping, the temperature was raised to 110 ° C., AIBN (0.3 g) and PMA (5.0 g) were added and reacted for 1 hour, and then AIBN (0.3 g) and PMA ( 5.0 g) was added and reacted for 1 hour, and AIBN (0.3 g) and PMA (5.0 g) were further added and reacted for 1 hour.

  The resulting reaction solution was cooled to room temperature, PMA (120.0 g) was added, and a binder resin solution having a nonvolatile content of 40% was obtained. The binder resin had a weight average molecular weight (Mw) of 12,700, a molecular weight distribution (PDI) of 1.88, and an acid value of 130 mgKOH / g.

Example 1
10 parts by mass of pigment, block copolymer No. 1 is 3 parts by mass, binder resin is 3 parts by mass, and PMA is 84 parts by mass. A 0.3 mm zirconia bead is added to 500 parts by mass. ) For 2 hours and sufficiently dispersed. After the dispersion was completed, the beads were filtered to obtain a colored composition. The pigment includes C.I. I. Pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals) was used. The viscosity of the obtained colored composition was evaluated. The results are shown in Table 3.

  Furthermore, the coloring composition for color filters was prepared with the compounding composition used as 40 mass parts of obtained coloring compositions, 26 mass parts of binder resin, and 34 mass parts of PMA. The alkali developability of the obtained color filter coloring composition was evaluated. The results are shown in Table 3.

(Examples 2-7 and Comparative Examples 1-4)
In the same manner as in the preparation method of Example 1, coloring compositions of Examples 2 to 7 and Comparative Examples 1 to 4, and a coloring composition for a color filter were prepared. The evaluation results of these viscosities and alkali developability are shown in Tables 3 and 4.

The coloring compositions of Examples 1 to 7 include, as a dispersant, an A block containing 60% by mass or more of the structural unit represented by Formula (1), and a B block containing the structural unit represented by Formula (2). Have
A block copolymer having an acid value of less than 10 mgKOH / g is used. Each of these coloring compositions has a low viscosity. Moreover, the coloring composition for color filters prepared using these coloring compositions had a short development time and was excellent in alkali developability.

  The coloring compositions of Comparative Examples 1 to 3 include, as a dispersant, an A block containing 60% by mass or more of a structural unit represented by Formula (1), and a B block containing a structural unit represented by Formula (2). And a block copolymer having an acid value of 10 mgKOH / g or more is used. All of these coloring compositions had high viscosity.

  The coloring composition of Comparative Example 4 includes, as a dispersant, an A block containing 60% by mass or more of the structural unit represented by the formula (1) and a B block not containing the structural unit represented by the formula (2). And a block copolymer having an acid value of 10 mgKOH / g or more is used. This colored composition had a high viscosity.

  The block copolymer of this invention can be used as a dispersing agent of the coloring agent of a coloring composition. The colored composition can be suitably used for a color filter. The color filter has high dimensional accuracy and can be suitably used for a color liquid crystal display element, a color image pickup tube element, a color sensor, an organic EL display element, electronic paper, and the like.

Claims (13)

A block containing 60% by mass or more of a structural unit represented by the following formula (1), and a B block containing a structural unit represented by the following formula (2),
A block copolymer having an acid value of less than 10 mgKOH / g.

[In Formula (1), n is an integer of 1-10. R ¹¹ is a hydrogen atom or a methyl group. R ¹² is an alkylene group having 1 to 10 carbon atoms. R ¹³ is an alkylene group having 1 to 10 carbon atoms. ]

[In the formula (2), R ²¹ represents a hydrogen atom or a methyl group. R ²² , R ²³ and R ²⁴ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ²² , R ²³ and R ²⁴ may be bonded to each other to form a cyclic structure. Y ² represents a divalent linking group. Z ⁻ represents a counter ion. ]   The block copolymer according to claim 1, which has an amine value of 10 mgKOH / g to 250 mgKOH / g. The block copolymer according to claim 1 or 2, wherein the B block further contains a structural unit represented by the formula (3).

[In the formula (3), R ³¹ represents a hydrogen atom or a methyl group. R ³² and R ³³ each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R ³² and R ³³ may be bonded to each other to form a cyclic structure. Y ³ represents a divalent linking group. ]   It is an AB type block copolymer, The block copolymer as described in any one of Claims 1-3.   The block copolymer as described in any one of Claims 1-4 whose content rate of the structural unit represented by the said Formula (1) is 60 mass%-90 mass% in 100 mass% of said A blocks. .   The block copolymer according to any one of claims 1 to 5, wherein the content of the structural unit represented by the formula (2) is 10% by mass to 50% by mass in 100% by mass of the B block. .   The block copolymer as described in any one of Claims 1-6 whose content rate of the said A block is 50 mass%-90 mass% in 100 mass% of block copolymers.   The block copolymer according to any one of claims 1 to 7, wherein a molecular weight distribution (PDI) of the block copolymer is 2.0 or less.   The block copolymer according to any one of claims 1 to 8, wherein the block copolymer is polymerized by living radical polymerization.   The dispersing agent characterized by including the block copolymer as described in any one of Claims 1-9.   A coloring composition comprising the dispersant according to claim 10, a colorant, a dispersion medium, and a binder resin.   The coloring composition according to claim 11, which is used for a color filter.   A color filter comprising a colored layer formed using the colored composition according to claim 12.